CA2912537C - Permanganate based conversion coating compositions - Google Patents
Permanganate based conversion coating compositions Download PDFInfo
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- CA2912537C CA2912537C CA2912537A CA2912537A CA2912537C CA 2912537 C CA2912537 C CA 2912537C CA 2912537 A CA2912537 A CA 2912537A CA 2912537 A CA2912537 A CA 2912537A CA 2912537 C CA2912537 C CA 2912537C
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D5/00—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/48—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 not containing phosphates, hexavalent chromium compounds, fluorides or complex fluorides, molybdates, tungstates, vanadates or oxalates
- C23C22/56—Treatment of aluminium or alloys based thereon
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/14—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to metal, e.g. car bodies
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/50—Multilayers
- B05D7/52—Two layers
- B05D7/54—No clear coat specified
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/60—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using alkaline aqueous solutions with pH greater than 8
- C23C22/66—Treatment of aluminium or alloys based thereon
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/68—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous solutions with pH between 6 and 8
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/82—After-treatment
- C23C22/83—Chemical after-treatment
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
- C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
- C23G1/02—Cleaning or pickling metallic material with solutions or molten salts with acid solutions
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
- C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
- C23G1/14—Cleaning or pickling metallic material with solutions or molten salts with alkaline solutions
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
- C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
- C23G1/14—Cleaning or pickling metallic material with solutions or molten salts with alkaline solutions
- C23G1/22—Light metals
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
- C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
- C23G1/24—Cleaning or pickling metallic material with solutions or molten salts with neutral solutions
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- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Paints Or Removers (AREA)
- Detergent Compositions (AREA)
- Chemical Treatment Of Metals (AREA)
- Preventing Corrosion Or Incrustation Of Metals (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
- Laminated Bodies (AREA)
- Other Surface Treatments For Metallic Materials (AREA)
Abstract
A composition for application to a substrate comprising a carrier, a permanganate ion source, and a corrosion inhibitor comprising a rare earth ion; an alkali metal ion, an alkaline earth metal ion, and/or a transition metal ion is disclosed.
A substrate or article including the composition for application to a substrate, and a method of treating a substrate comprising applying the composition to a substrate to form a permanganate treated surface of the substrate, arid applying a lithium containing composition on the permanganate treated surface are also disclosed.
A substrate or article including the composition for application to a substrate, and a method of treating a substrate comprising applying the composition to a substrate to form a permanganate treated surface of the substrate, arid applying a lithium containing composition on the permanganate treated surface are also disclosed.
Description
PERMANGANATE BASED CONVERSION COATING COMPOSITIONS
CROSS-REFERENCE TO RELATED APPLICATION
[0001] This application claims priority to and the benefit of U.S.
Provisional Application Serial No. 61/823,288, filed in the United States Patent and Trademark Office on May 14, 2013.
BACKGROUND
CROSS-REFERENCE TO RELATED APPLICATION
[0001] This application claims priority to and the benefit of U.S.
Provisional Application Serial No. 61/823,288, filed in the United States Patent and Trademark Office on May 14, 2013.
BACKGROUND
[0002] The oxidation and degradation of metals used in aerospace, commercial, and private industries are serious and costly problems. To prevent or reduce the oxidation and degradation of the metals used in these applications, a protective coating can be applied to the metal surface. This protective coating may be the only coating applied to the metal, or other coatings can be applied to further protect the metal surface.
[0003] Corrosion resistant coatings are known in the art of metal finishing, and older technologies involve chromium based coatings which have an undesirable environmental impact. Other corrosion resistant coatings are also known, including some chromium free coatings and/or pre-treatment coatings that may prevent or reduce oxidation and degradation of metals and aid in corrosion resistance.
Metal surface coatings that can provide corrosion resistance and also aid in the prevention or reduction of oxidation and degradation are desired.
SUMMARY
Metal surface coatings that can provide corrosion resistance and also aid in the prevention or reduction of oxidation and degradation are desired.
SUMMARY
[0004] According to embodiments of the present invention, a composition for application to a substrate comprises a carrier, a permanganate anion source, and a corrosion inhibitor comprising a rare earth ion, an alkali metal ion, an alkaline earth RECU 13/05/2015 22:01 0041223388270 PST
To. Page 9 of 58 2015-05-13 16:03:14 EDT
10036394262 From: Christine Graff PCl/US2014/037695 Replacement Sheet metal ion, and/or a transition metal ion. Methods for using the composition and articles coated therewith are also within the scope of the present invention.
DETAILED DESCRIPTION
1001:15) According to embodiments of the present invention, a composition for application to a metal substrate comprises a canier, a permanganate anion source, and a corrosion inhibitor comprising a metal cation. In some embodiments, the metal cation comprises a rare earth species (e.g., Cc (cerium) and/or Y (yttrium) cations), a transition metal species (e.g., Zr (zirconium), Zn (zinc) and/or Ti (titanium), a Group ILA (or Group 2) metal cation (e.g., Mg) and/or a Group LA (or Group 1) metal cation (e.g., Li (lithium)). In some embodiments, the metal cation may include Cr (chromium). However, in other embodiments, the composition is substantially chromium-free. As used herein, the term. "substantially" is used as a term of approximation and not as a term of degree. Additionally, the term "substantially chromium-free" is used as a term of approximation to denote that the amount of chromium in the composition is negligible, such that if chromium is present in the composition at all, it is as an incidental impurity. According to some embodiments, the metal cation is provided in the composition in the form of a salt, and the salt may comprise, for example, nitrate or carbonate counter ions.
[0006] As used herein, the following terms and variations thereof have the meanings given below, unless a different meaning is clearly intended by the context in which such term is used.
[00071 The terms "a," "an," and "the" and similar referents used herein are to be construed to cover both the singular and the plural unless their usage in context indicates otherwise.
[00081 As used in this disclosure, the term "comprise" and variations of the term, such as "comprising" and "comprises," are not intended to exclude other additives, components, integers ingredients or steps.
-2- =
REQ., 13/05/2015 2231 0041223388270 PST
To: Page 10 of 58 2015-05-13 16:03:14 EDT
10036394262 From: Christine Graff PCULIS2014/037695 Replacement Sheet [00091 The term "substrate," as used herein, refers to a material having a surface.
In reference to applying a conversion coating, the term "substrate" refers to a metal substrate such as aluminum, iron, copper, zinc, nickel, magnesium, and/or an alloy of any of these metals including but not limited to steel. Some exemplary substrates include aluminum and aluminum alloys. Additional exemplary substrates include high copper aluminum substrates (i.e., substrates including an alloy containing both aluminum and copper in which the amount of copper in the alloy is high, for example, an amount of copper in the alloy of 3 to 4%).
10010] The term "coating," and like terms, when used as a verb herein, refers to the process of applying a composition, i.e., contacting a substrate with a composition, such as contacting a substrate with a conversion coating, primer, and/or topcoat. The term "co: _______ tine may be used interchangeably with the terms "application/applying,"
"treatment/treating" or "pretreatment/pretreating", and may also be used to indicate various forms of application or treatment, such as painting, spraying and dipping (e.g., immersion, spraying, or spreading using a brush, roller, or the like), where a substrate is contacted with a composition by such application means. With regard to application via spraying, conventional (automatic or manual) spray techniques and equipment used for air spraying can be used. The composition can be applied in paste or gel form. The composition may be applied in any suitable thickness, depending on the application requirements. More than one coat of the composition may be applied.
All or part of the substrate can be contacted. That is, the compositions of the present invention can be applied to at least a portion of a substrate.
100111 The term "conversion coating," also referred to herein as a "conversion treatment" or "pretreatment," refers to a treatment for a metal substrate that causes the chemistry of the metal surface to be converted to a different surface chemistry. The terms "conversion treatment" and "conversion coating" also refer to the application or treatment of a metal surface in which a metal substrate is contacted with an aqueous solution having a metal of a different element than the metal contained in the RECU 13/05/2015 22:01 004122338827a PST
To: Page 11 of 58 2015-05-131603:14 EDT
10036394262 From: Christine Graff PCT/U S2014/037695 Replacement Sheet substrate. Additionally, the terms "conversion coating" and "conversion treatment"
refer to an aqueous solution having a metal element in contact with a metal substrate of a different element, in which the surface of the substrate partially dissolves in the aqueous solution, leading to the precipitation of a coating on the metal substrate (optionally using an external driving force to deposit the coating on the metal =
substrate). The resulting film is thus a combination of both the metal(s) in solution as -well as the metal(s) of the metallic substrate.
[00121 The term "salt," as used herein, refers to an ionically bonded inorganic compound and/or the ionized anion and cation of one or more inorganic compounds in solution.
[0013] As used herein, the term "permanganate" refers to a salt containing the manganate (VII) ion (Mn04). Exemplary permanganate compounds include ammonium permanganate (NI-L4Mn04), potassium permanganate (1(Mn04), and sodium permanganate (NaMn04).
[00141 The terra "rare earth element," as used herein, refers to an element in Group MB (or the lanthanide series) of the periodic table of the elements or yttrium.
The group of elements known as the rare earth elements includes, for example, elements 57-71 (i.e., La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tin, Yb and Lu) and yttrium. In some embodiments, however, as noted below, the term rare earth element may refer to La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu and Y.
[0015] The term "Group IA metal ion," or "Group 1 metal ion" and like terms, as used herein, refer to an ion or ions of elements from the first column of the periodic table (with the exception of H). The group of elements identified by Group IA
or Group 1 (with the exception of H) is also known as the alkali metals, and includes, for example, Li, Na, K, Rh, Cs, and Fr.
[00161 The term "Group HA metal ion," or "Group 2 metal ion" and like terms, as used herein, refer to an ion or ions of elements from the second column of the periodic table. The group of elements identified by Group LEA or Group 2 is also RECU 13/05/2015 22:01 0041223388270 PST
To: Page 12 of 58 2015-05-13 16:03:14 EDT
10036394262 From: Christine Graff PCMS2014/037695 Replacement Sheet known as the alkaline earth metals, and includes, for example, Be, Mg, Ca, Sr, Ba and Ra.
100171 The term "solution" refers to a composition comprising a solvent and a solute, and includes true solutions and suspensions. Examples of solutions include a solid, liquid or gas dissolved in a liquid and particulates or micelles suspended in a liquid.
[00181 All amounts disclosed herein are given in weight percent of the total weight of the composition at 25 C and one atmosphere pressure, unless otherwise indicated.
Permanganate compositions 100191 According to some embodiments of the present invention, a permanganate-containing composition for application to a metal substrate (e.g., a substrate comprising aluminum, magnesium, iron, zinc, nickel, and/or an alloy thereof) comprises a permanganate anion source, a corrosion inhibitor comprising a metal cation, and a carrier. The permanganate-containing compositions described herein can be used without borates, halides, or at elevated temperatures. In addition, the permanganate-containing compositions are compatible with alkaline and acidic deoxidizers; they do not require pm-exposure of the substrate with, e.g., lithium nitrate; nor do they require pre-treatment by elevated temperature water immersion.
[0020] The permanganate source may comprise a pennanganate salt or a combination of permanganate salts. The permanganate salt may include any alkali metal (i.e., Group IA or Group 1) cation, alkaline earth metal (i.e., Group I
lA or Group 2) cation, or an ammonium cation in addition to the manganate anion. For example, in some embodiments, the alkali or alkaline earth metal cation may comprise Li, Na, K, Rh, Cs, Fr, Be, Mg, Ca, Sr, Ba and/or Ra. In some embodiments, the alkali metal or alkaline earth metal cation comprises Li, Na, K, Rb, Cs, Be, Mg, Ca, Sr and/or Ba. For example, in some embodiments, the rare earth element comprises Na, K, Mg and/or Ca. Some nonlimiting examples of suitable permanganate sources include permanganate salts such as potassium permanganate,
To. Page 9 of 58 2015-05-13 16:03:14 EDT
10036394262 From: Christine Graff PCl/US2014/037695 Replacement Sheet metal ion, and/or a transition metal ion. Methods for using the composition and articles coated therewith are also within the scope of the present invention.
DETAILED DESCRIPTION
1001:15) According to embodiments of the present invention, a composition for application to a metal substrate comprises a canier, a permanganate anion source, and a corrosion inhibitor comprising a metal cation. In some embodiments, the metal cation comprises a rare earth species (e.g., Cc (cerium) and/or Y (yttrium) cations), a transition metal species (e.g., Zr (zirconium), Zn (zinc) and/or Ti (titanium), a Group ILA (or Group 2) metal cation (e.g., Mg) and/or a Group LA (or Group 1) metal cation (e.g., Li (lithium)). In some embodiments, the metal cation may include Cr (chromium). However, in other embodiments, the composition is substantially chromium-free. As used herein, the term. "substantially" is used as a term of approximation and not as a term of degree. Additionally, the term "substantially chromium-free" is used as a term of approximation to denote that the amount of chromium in the composition is negligible, such that if chromium is present in the composition at all, it is as an incidental impurity. According to some embodiments, the metal cation is provided in the composition in the form of a salt, and the salt may comprise, for example, nitrate or carbonate counter ions.
[0006] As used herein, the following terms and variations thereof have the meanings given below, unless a different meaning is clearly intended by the context in which such term is used.
[00071 The terms "a," "an," and "the" and similar referents used herein are to be construed to cover both the singular and the plural unless their usage in context indicates otherwise.
[00081 As used in this disclosure, the term "comprise" and variations of the term, such as "comprising" and "comprises," are not intended to exclude other additives, components, integers ingredients or steps.
-2- =
REQ., 13/05/2015 2231 0041223388270 PST
To: Page 10 of 58 2015-05-13 16:03:14 EDT
10036394262 From: Christine Graff PCULIS2014/037695 Replacement Sheet [00091 The term "substrate," as used herein, refers to a material having a surface.
In reference to applying a conversion coating, the term "substrate" refers to a metal substrate such as aluminum, iron, copper, zinc, nickel, magnesium, and/or an alloy of any of these metals including but not limited to steel. Some exemplary substrates include aluminum and aluminum alloys. Additional exemplary substrates include high copper aluminum substrates (i.e., substrates including an alloy containing both aluminum and copper in which the amount of copper in the alloy is high, for example, an amount of copper in the alloy of 3 to 4%).
10010] The term "coating," and like terms, when used as a verb herein, refers to the process of applying a composition, i.e., contacting a substrate with a composition, such as contacting a substrate with a conversion coating, primer, and/or topcoat. The term "co: _______ tine may be used interchangeably with the terms "application/applying,"
"treatment/treating" or "pretreatment/pretreating", and may also be used to indicate various forms of application or treatment, such as painting, spraying and dipping (e.g., immersion, spraying, or spreading using a brush, roller, or the like), where a substrate is contacted with a composition by such application means. With regard to application via spraying, conventional (automatic or manual) spray techniques and equipment used for air spraying can be used. The composition can be applied in paste or gel form. The composition may be applied in any suitable thickness, depending on the application requirements. More than one coat of the composition may be applied.
All or part of the substrate can be contacted. That is, the compositions of the present invention can be applied to at least a portion of a substrate.
100111 The term "conversion coating," also referred to herein as a "conversion treatment" or "pretreatment," refers to a treatment for a metal substrate that causes the chemistry of the metal surface to be converted to a different surface chemistry. The terms "conversion treatment" and "conversion coating" also refer to the application or treatment of a metal surface in which a metal substrate is contacted with an aqueous solution having a metal of a different element than the metal contained in the RECU 13/05/2015 22:01 004122338827a PST
To: Page 11 of 58 2015-05-131603:14 EDT
10036394262 From: Christine Graff PCT/U S2014/037695 Replacement Sheet substrate. Additionally, the terms "conversion coating" and "conversion treatment"
refer to an aqueous solution having a metal element in contact with a metal substrate of a different element, in which the surface of the substrate partially dissolves in the aqueous solution, leading to the precipitation of a coating on the metal substrate (optionally using an external driving force to deposit the coating on the metal =
substrate). The resulting film is thus a combination of both the metal(s) in solution as -well as the metal(s) of the metallic substrate.
[00121 The term "salt," as used herein, refers to an ionically bonded inorganic compound and/or the ionized anion and cation of one or more inorganic compounds in solution.
[0013] As used herein, the term "permanganate" refers to a salt containing the manganate (VII) ion (Mn04). Exemplary permanganate compounds include ammonium permanganate (NI-L4Mn04), potassium permanganate (1(Mn04), and sodium permanganate (NaMn04).
[00141 The terra "rare earth element," as used herein, refers to an element in Group MB (or the lanthanide series) of the periodic table of the elements or yttrium.
The group of elements known as the rare earth elements includes, for example, elements 57-71 (i.e., La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tin, Yb and Lu) and yttrium. In some embodiments, however, as noted below, the term rare earth element may refer to La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu and Y.
[0015] The term "Group IA metal ion," or "Group 1 metal ion" and like terms, as used herein, refer to an ion or ions of elements from the first column of the periodic table (with the exception of H). The group of elements identified by Group IA
or Group 1 (with the exception of H) is also known as the alkali metals, and includes, for example, Li, Na, K, Rh, Cs, and Fr.
[00161 The term "Group HA metal ion," or "Group 2 metal ion" and like terms, as used herein, refer to an ion or ions of elements from the second column of the periodic table. The group of elements identified by Group LEA or Group 2 is also RECU 13/05/2015 22:01 0041223388270 PST
To: Page 12 of 58 2015-05-13 16:03:14 EDT
10036394262 From: Christine Graff PCMS2014/037695 Replacement Sheet known as the alkaline earth metals, and includes, for example, Be, Mg, Ca, Sr, Ba and Ra.
100171 The term "solution" refers to a composition comprising a solvent and a solute, and includes true solutions and suspensions. Examples of solutions include a solid, liquid or gas dissolved in a liquid and particulates or micelles suspended in a liquid.
[00181 All amounts disclosed herein are given in weight percent of the total weight of the composition at 25 C and one atmosphere pressure, unless otherwise indicated.
Permanganate compositions 100191 According to some embodiments of the present invention, a permanganate-containing composition for application to a metal substrate (e.g., a substrate comprising aluminum, magnesium, iron, zinc, nickel, and/or an alloy thereof) comprises a permanganate anion source, a corrosion inhibitor comprising a metal cation, and a carrier. The permanganate-containing compositions described herein can be used without borates, halides, or at elevated temperatures. In addition, the permanganate-containing compositions are compatible with alkaline and acidic deoxidizers; they do not require pm-exposure of the substrate with, e.g., lithium nitrate; nor do they require pre-treatment by elevated temperature water immersion.
[0020] The permanganate source may comprise a pennanganate salt or a combination of permanganate salts. The permanganate salt may include any alkali metal (i.e., Group IA or Group 1) cation, alkaline earth metal (i.e., Group I
lA or Group 2) cation, or an ammonium cation in addition to the manganate anion. For example, in some embodiments, the alkali or alkaline earth metal cation may comprise Li, Na, K, Rh, Cs, Fr, Be, Mg, Ca, Sr, Ba and/or Ra. In some embodiments, the alkali metal or alkaline earth metal cation comprises Li, Na, K, Rb, Cs, Be, Mg, Ca, Sr and/or Ba. For example, in some embodiments, the rare earth element comprises Na, K, Mg and/or Ca. Some nonlimiting examples of suitable permanganate sources include permanganate salts such as potassium permanganate,
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10036394262 From: Christine Graff PCT/US2014/037695 Replacement Sheet sodium permanganate and ammonium permanganate.
100211 In some embodiments, the composition may be an aqueous coating composition, and the composition may therefore further include an aqueous carrier which may optionally comprise one or more organic solvents. Nonlimiting examples of suitable such solvents include propylene glycol, ethylene glycol, glycerol, low molecular weight alcohols, and the like. When used, the organic solvent may be present in the composition in an amount of 30 g solvent per 12 liters of composition to 400 g solvent per 12 liters of composition, with the remainder of the carrier being water. For example, in some embodiments, the organic solvent may be present in the composition in an amount of 100 g solvent per 12 liters of composition to 200 g solvent per 12 liters of composition, for example 107 g solvent per 12 liters of composition, with the remainder of the carrier being water. In some embodiments, however, the aqueous carrier is primarily water, e.g., deionized water, The aqueous carrier is provided in an amount sufficient to provide the composition with the concentrations of the metal ions and permanganate sources described herein.
10022] The concentration of the permanganate source in the composition may be 0.008 percent by weight up to the solubility limit of the permanganate source in the carrier. In some embodiments, the permanganate source may be present in the =
composition inc concentration of 0.01% to 6.0% by weight. For example, in some embodiments, the permanganate source may be present in the composition in a concentration of 0.0375% to 0.15% by weight.
[0023] As noted above, the permanganate containing composition may further comprise a corrosion inhibitor comprising a metal cation. The metal cation may comprise one or more of various metal cations which have corrosion inhibiting characteristics. For example, in some embodiments, the metal cation may comprise a rare earth element, such as, for example, La, Ce, Pr, Nd, Pm, Sin, Eu, Gd, Tb, Dy, Er, Tm, Yb, Lu. In some embodiments, the rare earth element comprises La, Ce, Pr, Nd, Sm, En, Gd, Tb, Dy=, Ho, Er, Tm, Yb, Lu and/or Y. For example, in some embodiments, thc rare earth element comprises Ce, Y. Pr and/or Nd. Other suitable
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10036394262 From: Christine Graff PCT/US2014/037695 Replacement Sheet sodium permanganate and ammonium permanganate.
100211 In some embodiments, the composition may be an aqueous coating composition, and the composition may therefore further include an aqueous carrier which may optionally comprise one or more organic solvents. Nonlimiting examples of suitable such solvents include propylene glycol, ethylene glycol, glycerol, low molecular weight alcohols, and the like. When used, the organic solvent may be present in the composition in an amount of 30 g solvent per 12 liters of composition to 400 g solvent per 12 liters of composition, with the remainder of the carrier being water. For example, in some embodiments, the organic solvent may be present in the composition in an amount of 100 g solvent per 12 liters of composition to 200 g solvent per 12 liters of composition, for example 107 g solvent per 12 liters of composition, with the remainder of the carrier being water. In some embodiments, however, the aqueous carrier is primarily water, e.g., deionized water, The aqueous carrier is provided in an amount sufficient to provide the composition with the concentrations of the metal ions and permanganate sources described herein.
10022] The concentration of the permanganate source in the composition may be 0.008 percent by weight up to the solubility limit of the permanganate source in the carrier. In some embodiments, the permanganate source may be present in the =
composition inc concentration of 0.01% to 6.0% by weight. For example, in some embodiments, the permanganate source may be present in the composition in a concentration of 0.0375% to 0.15% by weight.
[0023] As noted above, the permanganate containing composition may further comprise a corrosion inhibitor comprising a metal cation. The metal cation may comprise one or more of various metal cations which have corrosion inhibiting characteristics. For example, in some embodiments, the metal cation may comprise a rare earth element, such as, for example, La, Ce, Pr, Nd, Pm, Sin, Eu, Gd, Tb, Dy, Er, Tm, Yb, Lu. In some embodiments, the rare earth element comprises La, Ce, Pr, Nd, Sm, En, Gd, Tb, Dy=, Ho, Er, Tm, Yb, Lu and/or Y. For example, in some embodiments, thc rare earth element comprises Ce, Y. Pr and/or Nd. Other suitable
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10036394262 From: Christine Graff PCT/U S2014/037695 Replacement Sheet metal cations include Group IA (or Group I) or Group IIA (or Group 2) metal cations (i.e., the alkali metals and alkaline earth metals). For example, in some embodiments, the metal cation may comprise an alkali metal, such as, for example, Li, Na, K, Rb, Cs and/or Fr, and/or an alkaline earth metal, such as, for example, Be, Mg, Ca, Sr, Ba and/or Ra. Other suitable metal cations include transition metal cations (e.g., Zr and/or Zn). Also, as discussed above, in some embodiments, the metal cation may include Cr (chromium). However, in other embodiments, the composition is substantially chromitun-free. As used herein, the term "substantially" is used as .a term of approximation and not as a term of degree. Additionally, the term "substantially chromium-free" is used as a term of approximation to denote that the amount of chromium in the composition is negligible, such that if chromium is present in the composition at all, it is as an incidental impurity. In some embodiments, for example, the metal cation may comprise Ce, Y, Pr, Nd, Zr, Zn, Li, Na, K and/or Mg. In some example embodiments, the metal cation comprises an alkali metal, such as, for example, Li, Na, K, Rb and/or Cs, and/or an alkaline earth metal, such as, for example, Be, Mg, Ca, Sr and/or Ba. In some embodiments, for example, the metal cation comprises lithium, sodium, potassium, and/or magnesium.
In other embodiments, the metal cation comprises Ce, Y, Nd and/or Li. ) or transition metal cations (e.g., Zr and/or Zn). In some embodiments, for example, the metal cation may comprise Ce, Y, Pr, Nd, Zr, Zn, Li, Na, K and/or Mg.
[0024] The metal cation can be present in the composition at a concentration of 0.0008 and 0.2 percent by weight of the composition. For example, in some embodiments, the metal cation may be present in the composition at a concentration of 0.002 and 0.004 percent by weight. In some embodiments, for example, the metal cation can be present in the composition at a concentration of 0.05 g per liter of composition to 25 g per liter of composition. For example, in some embodiments, the metal cation can be present in the composition at a concentration of 0.05 g per liter of composition to 16 g per liter of composition. In some embodiments, for example, the metal cation can be present in the composition at a concentration of 0.1 g per liter of
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10036394262 From: Christine Graff PCT/U S2014/037695 Replacement Sheet metal cations include Group IA (or Group I) or Group IIA (or Group 2) metal cations (i.e., the alkali metals and alkaline earth metals). For example, in some embodiments, the metal cation may comprise an alkali metal, such as, for example, Li, Na, K, Rb, Cs and/or Fr, and/or an alkaline earth metal, such as, for example, Be, Mg, Ca, Sr, Ba and/or Ra. Other suitable metal cations include transition metal cations (e.g., Zr and/or Zn). Also, as discussed above, in some embodiments, the metal cation may include Cr (chromium). However, in other embodiments, the composition is substantially chromitun-free. As used herein, the term "substantially" is used as .a term of approximation and not as a term of degree. Additionally, the term "substantially chromium-free" is used as a term of approximation to denote that the amount of chromium in the composition is negligible, such that if chromium is present in the composition at all, it is as an incidental impurity. In some embodiments, for example, the metal cation may comprise Ce, Y, Pr, Nd, Zr, Zn, Li, Na, K and/or Mg. In some example embodiments, the metal cation comprises an alkali metal, such as, for example, Li, Na, K, Rb and/or Cs, and/or an alkaline earth metal, such as, for example, Be, Mg, Ca, Sr and/or Ba. In some embodiments, for example, the metal cation comprises lithium, sodium, potassium, and/or magnesium.
In other embodiments, the metal cation comprises Ce, Y, Nd and/or Li. ) or transition metal cations (e.g., Zr and/or Zn). In some embodiments, for example, the metal cation may comprise Ce, Y, Pr, Nd, Zr, Zn, Li, Na, K and/or Mg.
[0024] The metal cation can be present in the composition at a concentration of 0.0008 and 0.2 percent by weight of the composition. For example, in some embodiments, the metal cation may be present in the composition at a concentration of 0.002 and 0.004 percent by weight. In some embodiments, for example, the metal cation can be present in the composition at a concentration of 0.05 g per liter of composition to 25 g per liter of composition. For example, in some embodiments, the metal cation can be present in the composition at a concentration of 0.05 g per liter of composition to 16 g per liter of composition. In some embodiments, for example, the metal cation can be present in the composition at a concentration of 0.1 g per liter of
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10036394262 From: Christine Graff PCUUS2014/037695 Replacement Sheet composition to 10 g per liter of composition. For example, in some embodiments, the metal cation can be present in the composition at a concentration of Ig per liter of composition to 5 g per liter of composition. For example, when the metal cation includes a rare earth cation, the rare earth cation may be present at a concentration of 0.05 g per liter of composition to 25 g per liter of composition, or 0.1 g per liter of composition to 10 g per liter of composition. When the metal cation Mendes an alkali = metal or alkaline earth metal cation, the alkali metal or alkaline earth metal cation . may be present at a concentration of 0.05 g per liter of composition to 16 g per liter of composition, or 1 g per liter of composition to 5 g per liter of composition.
As discussed in further detail below, the metal cation may be provided in the composition in the form of a metal salt, in which case, the amounts listed here reflect the amount of the salt in the composition.
[0025] As noted above, the metal cation may be provided in the composition in the form of a salt (i.e., a metal salt may serve as the source for the metal cation in the composition) having an anion and the metal cation as the cation of the salt.
The anion of the salt may be any suitable anion capable of forming a salt with the rare earth elements, alkali metals, alkaline earth metals, and/or transition metals.
Nonlimiting examples of anions suitable for forming a salt with alkali metals, alkaline earth metals, transition metals and rare earth elements include carbonates, hydroxides, nitrates, halides (e.g., Cr, Bf, , r or F), sulfates, phosphates and silicates (e.g., orthosilicates and metasilicates). For example, the metal salt may comprise a carbonate, hydroxide, halide, nitrate, sulfate, phosphate and/or silicate (e.g., ortho silicate or metasilicatc) of Cr, Li, Na, K, Rb, Cs, Fr, Be, Mg, Ca, Sr, Ba, Ra, Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Od, Tb, Dy, Ho, Er, Tin, Yb, Lu, Sc, Ti, Zr, H Rf, V, Nb, Ta, Db, Cr, Mo, W, Sg, Mn, 'Fe, Re, Bh, Fe, Ru, Os, Hs, Co, Rh, Ii, Mt, Ni, Pd, Pt, Ds, Cu, Ag, Au, Itg, Zn, Cd, Hg and/or Co. In some embodiments for example, the metal salt may comprise a carbonate, hydroxide, halide, nitrate, sulfate, phosphate and/or silicate (e.g., orthosilicate or metasilicate) of Cr, Li, Na, K, Rb, Cs, Be, Mg, Ca, Sr, 13a, Y. La, Cc, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Sc, Ti, Zr,
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10036394262 From: Christine Graff PCUUS2014/037695 Replacement Sheet composition to 10 g per liter of composition. For example, in some embodiments, the metal cation can be present in the composition at a concentration of Ig per liter of composition to 5 g per liter of composition. For example, when the metal cation includes a rare earth cation, the rare earth cation may be present at a concentration of 0.05 g per liter of composition to 25 g per liter of composition, or 0.1 g per liter of composition to 10 g per liter of composition. When the metal cation Mendes an alkali = metal or alkaline earth metal cation, the alkali metal or alkaline earth metal cation . may be present at a concentration of 0.05 g per liter of composition to 16 g per liter of composition, or 1 g per liter of composition to 5 g per liter of composition.
As discussed in further detail below, the metal cation may be provided in the composition in the form of a metal salt, in which case, the amounts listed here reflect the amount of the salt in the composition.
[0025] As noted above, the metal cation may be provided in the composition in the form of a salt (i.e., a metal salt may serve as the source for the metal cation in the composition) having an anion and the metal cation as the cation of the salt.
The anion of the salt may be any suitable anion capable of forming a salt with the rare earth elements, alkali metals, alkaline earth metals, and/or transition metals.
Nonlimiting examples of anions suitable for forming a salt with alkali metals, alkaline earth metals, transition metals and rare earth elements include carbonates, hydroxides, nitrates, halides (e.g., Cr, Bf, , r or F), sulfates, phosphates and silicates (e.g., orthosilicates and metasilicates). For example, the metal salt may comprise a carbonate, hydroxide, halide, nitrate, sulfate, phosphate and/or silicate (e.g., ortho silicate or metasilicatc) of Cr, Li, Na, K, Rb, Cs, Fr, Be, Mg, Ca, Sr, Ba, Ra, Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Od, Tb, Dy, Ho, Er, Tin, Yb, Lu, Sc, Ti, Zr, H Rf, V, Nb, Ta, Db, Cr, Mo, W, Sg, Mn, 'Fe, Re, Bh, Fe, Ru, Os, Hs, Co, Rh, Ii, Mt, Ni, Pd, Pt, Ds, Cu, Ag, Au, Itg, Zn, Cd, Hg and/or Co. In some embodiments for example, the metal salt may comprise a carbonate, hydroxide, halide, nitrate, sulfate, phosphate and/or silicate (e.g., orthosilicate or metasilicate) of Cr, Li, Na, K, Rb, Cs, Be, Mg, Ca, Sr, 13a, Y. La, Cc, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Sc, Ti, Zr,
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10038394262 From: Christine Graff PCT/US2014/037695 Replacement Sheet Hf, V, Nb, Ta, Cr, Mo, W, Mn, To, Re, Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd and/or Hg. In some embodiments, for example, the metal salt may comprise a carbonate, hydroxide, halide, nitrate, sulfate, phosphate and/or silicate (e.g., orthosilicate or mettisilicatc) of Cr, Li, Na, K, Rb, Cs, Be, Mg, Ca, Sr, Ba, Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Sc, Ti, Zr, 1-If, V, Nb, Ta, Mo, W, Mn, Tc, Re, Ru, Os, Co, Rh, Ir, Pd, Pt, Ag, Au, Zn, Cd and/or Fig. For example, in some embodiments, the metal salt may comprise a carbonate, hydroxide, halide, nitrate, sulfate, phosphate and/or silicate (e.g., orthosilicate or metasilicate) of Cr, La, Ce, Y, Pr, Nd, Zr, Zn, Li, Na, K and/or Mg. In some embodiments, for example, the permanganate composition may include sodium hydroxide. Additionally, in some embodiments, the composition may include at least two metal salts, and the at least two metal salts may comprise different anions and/or cations from each other.
For example, the at least two metal salts may comprise different anions but the same cations, or may comprise different cations but the same anions. In some embodiments, for example, the metal cation is provided in the composition in the form of a metal salt such as a zinc salt, a zirconium salt, a titanium salt, a chromium salt, a lithium salt, and/or a rare earth salt. As no ted above, the zinc, zirconium, titanium, chromium, lithium, and/or rare earth salt may be present in the permanganate-containing composition at a concentration of 0.0008 to 0.2 percent by weight of the composition, for example 0.002 to 0.004 percent by weight of the composition.
100261 In some embodiments, the permanganate-containing composition may further comprise an azole compound. The azole compound may include cyclic compounds having 1 nitrogen atoms, such as pyrroles, 2 or more nitrogen atoms, such as pyrazoles, imidazoles, triazoles, tetrazoles and pentazoles, 1 nitrogen atom and I
oxygen atom, such as oxazoles and isoxazoles, and 1 nitrogen atom and 1 sulfur atom, such as thiazoles and isothiazoles. Nonlimiting examples of suitable azole compounds include 2,5-dimercapto-1,3,4-thiadiazole (CAS:1072-71-5), lEt-benzotriazolc (CAS: 95-14-7), 111-1,2,3-triazole (CAS: 288-36-8), 2-arnino-5-
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10038394262 From: Christine Graff PCT/US2014/037695 Replacement Sheet Hf, V, Nb, Ta, Cr, Mo, W, Mn, To, Re, Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd and/or Hg. In some embodiments, for example, the metal salt may comprise a carbonate, hydroxide, halide, nitrate, sulfate, phosphate and/or silicate (e.g., orthosilicate or mettisilicatc) of Cr, Li, Na, K, Rb, Cs, Be, Mg, Ca, Sr, Ba, Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Sc, Ti, Zr, 1-If, V, Nb, Ta, Mo, W, Mn, Tc, Re, Ru, Os, Co, Rh, Ir, Pd, Pt, Ag, Au, Zn, Cd and/or Fig. For example, in some embodiments, the metal salt may comprise a carbonate, hydroxide, halide, nitrate, sulfate, phosphate and/or silicate (e.g., orthosilicate or metasilicate) of Cr, La, Ce, Y, Pr, Nd, Zr, Zn, Li, Na, K and/or Mg. In some embodiments, for example, the permanganate composition may include sodium hydroxide. Additionally, in some embodiments, the composition may include at least two metal salts, and the at least two metal salts may comprise different anions and/or cations from each other.
For example, the at least two metal salts may comprise different anions but the same cations, or may comprise different cations but the same anions. In some embodiments, for example, the metal cation is provided in the composition in the form of a metal salt such as a zinc salt, a zirconium salt, a titanium salt, a chromium salt, a lithium salt, and/or a rare earth salt. As no ted above, the zinc, zirconium, titanium, chromium, lithium, and/or rare earth salt may be present in the permanganate-containing composition at a concentration of 0.0008 to 0.2 percent by weight of the composition, for example 0.002 to 0.004 percent by weight of the composition.
100261 In some embodiments, the permanganate-containing composition may further comprise an azole compound. The azole compound may include cyclic compounds having 1 nitrogen atoms, such as pyrroles, 2 or more nitrogen atoms, such as pyrazoles, imidazoles, triazoles, tetrazoles and pentazoles, 1 nitrogen atom and I
oxygen atom, such as oxazoles and isoxazoles, and 1 nitrogen atom and 1 sulfur atom, such as thiazoles and isothiazoles. Nonlimiting examples of suitable azole compounds include 2,5-dimercapto-1,3,4-thiadiazole (CAS:1072-71-5), lEt-benzotriazolc (CAS: 95-14-7), 111-1,2,3-triazole (CAS: 288-36-8), 2-arnino-5-
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10036394262 From: Christine Graff PCT/US2014/037695 Replacement Sheet mercapto-1,3,4-thiadiazole (CAS; 2349-67-9), also named 5-amino-1,3,4-thiadiazole-2-thiol, and 2-amino-1,3,4-thiadiazole (CAS: 4005-51-0). In some embodiments, for example, the azole compound comprises 2,5-dimercapto-1,3,4-tbiadiazole.
10027] The azole compound may be present in the composition at a concentration of 0.0005 g per liter of composition to 3 g per liter of composition. For example, in some embodiments, the azole compound may be present in the composition at a concentration of 0.004 g per liter of composition to 0.1 g per liter of composition. In some embodiments, the azole compound may be present in the composition at a concentration of 0.0008 to 0.2 weight percent, for example 0.002 to 0.004 weight percent.
[00281 In some embodiments, the composition may further comprise an oxidizing agent. Any suitable oxidizing agent may be used, nonlimiting examples of which include organic peroxides, such as benzoyl peroxides, ozone and nitrates. One =
nonlimiting example of a suitable oxidizing agent is hydrogen peroxide. In some embodiments, the oxidizing agent may be present in the composition in an amount of 0.001 wt% to 15 wt%. For example, in some embodiments the oxidizing agent may comprise a 30% solution of hydrogen peroxide present in an amount of 0.001 wt%
to 15 wt%, for example 0.002wt% to 0.006 wt%, or 0.008 wt% to 0.08 wt%. Addition of an oxidizing agent, such as hydrogen peroxide, to a permanganate-containing composition may cause the peroxide to decompose quickly, and therefore, caution should be used when adding an oxidizing agent to the permanganate-containing composition.
[00291 In some embodiments of the present invention, the pennanganate-containing composition may further comprise one or more additives for promoting corrosion resistance, adhesion to the metal substrate, adhesion of subsequent coatings, and/or to provide another desired aesthetic or functional effect. An additive, if used, may be present in the composition in an amount of 0.0001 weight percent up to weight percent based on the total weight of the composition. These optional additives may be chosen based on the desired function of the resulting coating and/or its
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10036394262 From: Christine Graff PCT/US2014/037695 Replacement Sheet mercapto-1,3,4-thiadiazole (CAS; 2349-67-9), also named 5-amino-1,3,4-thiadiazole-2-thiol, and 2-amino-1,3,4-thiadiazole (CAS: 4005-51-0). In some embodiments, for example, the azole compound comprises 2,5-dimercapto-1,3,4-tbiadiazole.
10027] The azole compound may be present in the composition at a concentration of 0.0005 g per liter of composition to 3 g per liter of composition. For example, in some embodiments, the azole compound may be present in the composition at a concentration of 0.004 g per liter of composition to 0.1 g per liter of composition. In some embodiments, the azole compound may be present in the composition at a concentration of 0.0008 to 0.2 weight percent, for example 0.002 to 0.004 weight percent.
[00281 In some embodiments, the composition may further comprise an oxidizing agent. Any suitable oxidizing agent may be used, nonlimiting examples of which include organic peroxides, such as benzoyl peroxides, ozone and nitrates. One =
nonlimiting example of a suitable oxidizing agent is hydrogen peroxide. In some embodiments, the oxidizing agent may be present in the composition in an amount of 0.001 wt% to 15 wt%. For example, in some embodiments the oxidizing agent may comprise a 30% solution of hydrogen peroxide present in an amount of 0.001 wt%
to 15 wt%, for example 0.002wt% to 0.006 wt%, or 0.008 wt% to 0.08 wt%. Addition of an oxidizing agent, such as hydrogen peroxide, to a permanganate-containing composition may cause the peroxide to decompose quickly, and therefore, caution should be used when adding an oxidizing agent to the permanganate-containing composition.
[00291 In some embodiments of the present invention, the pennanganate-containing composition may further comprise one or more additives for promoting corrosion resistance, adhesion to the metal substrate, adhesion of subsequent coatings, and/or to provide another desired aesthetic or functional effect. An additive, if used, may be present in the composition in an amount of 0.0001 weight percent up to weight percent based on the total weight of the composition. These optional additives may be chosen based on the desired function of the resulting coating and/or its
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10036394262 From: Christine Graff PCT/US2014/037695 Replacement Sheet application or intended use. Suitable additives may include a solid or liquid component admixed with the composition for the purpose of affecting one or more properties of the composition. The additive may include, for example, a surfactant, which can assist in wetting the metal substrate, and/or other additives that can assist in the development of a particular surface property, such as a rough or smooth surface.
Other nonlimiting examples of suitable additives include alcohols, co-inhibitors, lithium salts, flow control agents, thixotropic agents such as bentonite clay, gelatins, cellulose, anti-gassing agents, degreasing agents, anti-foaming agents, organic co-solvents, catalysts, dyes, amino acids, urea based compounds, complexing agents, valence stabilizers, and the like, as well as other customary auxiliaries.
Suitable additives are known in the art of formulating compositions for surface coatings and can be used in the compositions according to embodiments of the present invention, as would he understood by those of ordinary skill in the art with reference to this disclosure.
[0030] In some embodiments, the composition may additionally comprise a surfactant (such as, for example, an anionic, nonionic and/or cationic surfactant), mixture of surfactants, or detergent-type aqueous solution. Nonlimiting examples of some suitable commercially available surfactants include Dynol 604 and Carbowet DC-01 (both available from Air Products & Chemicals, Inc., Allentown, PA), and Triton X-100 (available from The Dow Chemical Company, Midland MI). The surfactant, mixture of surfactants, or detergent-type aqueous solution may be present in the composition in an amount of 0.0003 wt% to 3 wt.%, for example, 0.000375 wt%
to 1 wt%, or 0.02 wt/o. In one embodiment, the composition having a surfactant, mixture of surfactants, or detergent-type aqueous solution may be utilized to combine a metal substrate cleaning step and a conversion coating step in one process.
In another embodiment, the composition having a surfactant, mixture of surfactants, or detergent-type aqueous solution can additionally contain an oxidizing agent, as previously described herein.
[0031] The composition may also contain other components and additives such
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10036394262 From: Christine Graff PCT/US2014/037695 Replacement Sheet application or intended use. Suitable additives may include a solid or liquid component admixed with the composition for the purpose of affecting one or more properties of the composition. The additive may include, for example, a surfactant, which can assist in wetting the metal substrate, and/or other additives that can assist in the development of a particular surface property, such as a rough or smooth surface.
Other nonlimiting examples of suitable additives include alcohols, co-inhibitors, lithium salts, flow control agents, thixotropic agents such as bentonite clay, gelatins, cellulose, anti-gassing agents, degreasing agents, anti-foaming agents, organic co-solvents, catalysts, dyes, amino acids, urea based compounds, complexing agents, valence stabilizers, and the like, as well as other customary auxiliaries.
Suitable additives are known in the art of formulating compositions for surface coatings and can be used in the compositions according to embodiments of the present invention, as would he understood by those of ordinary skill in the art with reference to this disclosure.
[0030] In some embodiments, the composition may additionally comprise a surfactant (such as, for example, an anionic, nonionic and/or cationic surfactant), mixture of surfactants, or detergent-type aqueous solution. Nonlimiting examples of some suitable commercially available surfactants include Dynol 604 and Carbowet DC-01 (both available from Air Products & Chemicals, Inc., Allentown, PA), and Triton X-100 (available from The Dow Chemical Company, Midland MI). The surfactant, mixture of surfactants, or detergent-type aqueous solution may be present in the composition in an amount of 0.0003 wt% to 3 wt.%, for example, 0.000375 wt%
to 1 wt%, or 0.02 wt/o. In one embodiment, the composition having a surfactant, mixture of surfactants, or detergent-type aqueous solution may be utilized to combine a metal substrate cleaning step and a conversion coating step in one process.
In another embodiment, the composition having a surfactant, mixture of surfactants, or detergent-type aqueous solution can additionally contain an oxidizing agent, as previously described herein.
[0031] The composition may also contain other components and additives such
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10036394262 From: Christine Graff PCT/US2014/037695 Replacement Sheet as, but not limited to, carbonates, surfactants, chelators, thickeners, allantoin, polyvinylpyrrolidone, halides, and/or adhesion promoters. For example, in some embodiments, the composition may further comprise allantoin, polyvinylpyrrolidone, surfactants, and/or other additives and/or co-inhibitors.
[0032] In some embodiments, the composition may also contain an indicator compound, so named because they indicate, for example, the presence of a chemical species, such as a metal ion, the pH of a composition, and the like. An "indicator", "indicator compound", and like terms as used herein refer to a compound that changes color in response to some external stimulus, parameter, or condition, such as the presence of a metal ion, or in response to a specific pH or range of pHs.
[0033] The indicator compound used according to certain embodiments of the present invention can be any indicator known in the art that indicates the presence of a species, a particular pH, and the like. For example, a suitable indicator may be one that changes color after forming a metal ion complex with a particular metal ion. The metal ion indicator is generally a highly conjugated organic compound. A
"conjugated compound" as used herein, and as will be understood by those skilled in the art, refers to a compound having two double bonds separated by a single bond, for example two carbon-carbon double bonds with a single carbon-carbon bond between them. Any conjugated compound can be used according to the present invention.
[0034] Similarly, the indicator compound can be one in which the color changes upon change of the pH; for example, the compound may be one color at an acidic or neutral pH and change color in an alkaline pH, or vice versa. Such indicators are well known and widely commercially available. An indicator that "changes color when exposed to an alkaline pH" therefore has a first color (or is colorless) when exposed to an acidic or neutral pH and changes to a second color (or goes from colorless to colored) when exposed to an alkaline pH. Similarly, an indicator that "changes color when exposed to an acidic pH" goes from a first color/colorless to a second color/colored when the pH changes from alkaline/neutral to acidic.
[0035] Nonlimiting examples of such indicator compounds include methyl
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10036394262 From: Christine Graff PCT/US2014/037695 Replacement Sheet as, but not limited to, carbonates, surfactants, chelators, thickeners, allantoin, polyvinylpyrrolidone, halides, and/or adhesion promoters. For example, in some embodiments, the composition may further comprise allantoin, polyvinylpyrrolidone, surfactants, and/or other additives and/or co-inhibitors.
[0032] In some embodiments, the composition may also contain an indicator compound, so named because they indicate, for example, the presence of a chemical species, such as a metal ion, the pH of a composition, and the like. An "indicator", "indicator compound", and like terms as used herein refer to a compound that changes color in response to some external stimulus, parameter, or condition, such as the presence of a metal ion, or in response to a specific pH or range of pHs.
[0033] The indicator compound used according to certain embodiments of the present invention can be any indicator known in the art that indicates the presence of a species, a particular pH, and the like. For example, a suitable indicator may be one that changes color after forming a metal ion complex with a particular metal ion. The metal ion indicator is generally a highly conjugated organic compound. A
"conjugated compound" as used herein, and as will be understood by those skilled in the art, refers to a compound having two double bonds separated by a single bond, for example two carbon-carbon double bonds with a single carbon-carbon bond between them. Any conjugated compound can be used according to the present invention.
[0034] Similarly, the indicator compound can be one in which the color changes upon change of the pH; for example, the compound may be one color at an acidic or neutral pH and change color in an alkaline pH, or vice versa. Such indicators are well known and widely commercially available. An indicator that "changes color when exposed to an alkaline pH" therefore has a first color (or is colorless) when exposed to an acidic or neutral pH and changes to a second color (or goes from colorless to colored) when exposed to an alkaline pH. Similarly, an indicator that "changes color when exposed to an acidic pH" goes from a first color/colorless to a second color/colored when the pH changes from alkaline/neutral to acidic.
[0035] Nonlimiting examples of such indicator compounds include methyl
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10036394262 From: Christine Graff PCT/US2014/037695 Replacement Sheet orange, xylenol orange, catechol violet, bromophenol blue, green and purple, eriochrome black T, Celestine blue, hematoxylin, calmagite, gallocyanine, and combinations thereof. According to some embodiments, the indicator compound comprises an organic indicator compound that is a metal ion indicator.
Nonlimiting examples of indicator compounds include those found in Table 1. Fluorescent indicators, which will emit light in certain conditions, can also be used according to the present invention, although in certain embodiments the use of a fluorescent indicator is specifically excluded. That is, in certain embodiments, conjugated compounds that exhibit fluorescence are specifically excluded. As used herein, "fluorescent indicator" and like terms refer to compounds, molecules, pigments, and/or dyes that will fluoresce or otherwise exhibit color upon exposure to ultraviolet or visible light. To "fluoresce" will be understood as emitting light following absorption of light or other electromagnetic radiation_ Examples of such indicators, often referred to as "tags," include acridine, anthraquinone, coumarin, diphenylraethane, diphenylnaphthlymethane, quinoline, stilbene, triphenylmethane, anthmeine and/or molecules containing any of these moieties and/or derivatives of any of these such as rhodamines, phenanthridincs, oxazines, fluorones, cyanines and/or acridines.
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10036394262 From: Christine Graff PCTTUS2014/037695 Replacement Sheet TABLE I
CAS keg.
Compound Structure No.
Catechol Violet 115-41-3 . 0 Synonyms: OH , Catecholsullimphthalein; I
0=S=0 Pyrocatecholsulfonephthalein; HO
, Pyrocatechol Violet HO
Xylenol Orange o" 3618-43-7 Synonym: 0y0H
bis(carboxymethyl)aminomethyn- OHY
o-cresolsulfonephthalein tetrasodium salt Ho r,N,,A0H
[0036] According to one embodiment, the conjugated compound comprises catechol violet, as shown in Table I. Cateclaol violet (CV) is a sulfone phthalein dye made from condensing two moles of pyrocatechol with one mole of o-sulfobenzoic acid anhydride. It has been found that CV has indicator properties and when incorporated into corrosion resistant compositions having metal ions, it forms complexes, making it useful as a chelotnetric reagent. As the composition containing the CV chelates metal ions, a generally blue to blue-violet color is observed.
.
100371 According to another embodiment, xylenol orange, as shown in Table 1 is employed in the compositions according to embodiments of the present invention. It has been found that xylcnol orange has metal ion indicator properties and when incorporated into corrosion resistant compositions having metal ions, it forms complexes, making it useful as a chelometric reagent. As the composition containing the xylenol orange chelates metal ions, a solution of xylenol orange turns from red to a generally blue color.
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10036394262 From. Christine Graff PCT/US2014/037695 Replacement Sheet 100381 The indicator compound may be present in the composition in an amount of 0.01g/1000 g solution to 3 g/1000 g solution, such as 0.05g/1000 g solution to 0.1 g/1000 g solution.
100391 In some embodiments of the present invention, the conjugated compound, if it changes color in response to a certain external stimulus, provides a benefit when using the current compositions, in that it can serve as a visual indication that a substrate has been treated with the composition. For example, a composition comprising an indicator that changes color when exposed to a metal ion that is present in the substrate will change color upon complexing with metal ions in that substrate;
this allows the user to see that the substrate has been contacted with the composition.
Similar benefits can be realized by depositing an alkaline or acid layer on a substrate and contacting the substrate with a composition of the present invention that changes color when exposed to an alkaline or acidic pH.
[0040] In addition, the use of certain conjugated compounds according to embodiments of the present invention can provide the substrate with improved adhesion to subsequently applied coating layers. This is particularly true it' the conjugated compound has hydroxyl functionality. Accordingly, some embodiments of the present compositions allow for deposition of subsequent coating layers onto a substrate treated according to embodiments of the present invention without the need for a primer layer. Such coating layers can include urethane coatings and epoxy coatings.
[00411 The permanganate containing composition may have an alkaline, neutral or acidic pH. For example, in some embodiments, the permanganate containing composition may have a pH of 2 to 14. In some embodiments, for example, the permanganate composition may have a pH of 4 to 10.
[00421 In some embodiments, the permanganate containing composition may include 0.1 g to 60 g of a permanganate salt (e.g., K, Li, Na, etc.) and enough water to make 1 L of solution. According to some embodiments, for example, the RECU 13/05/2015 22:01 0041223388270 PST
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10036394262 From: Christine Graff PCT/US2014/037695 Replacement Sheet permanganate composition may include 0.375 g to 7.5 g (e.g., 0.375g to 2.5g) of the permanganate salt, and enough water to make 1 L of solution.
100431 In other embodiments, the permanganate containing composition may further include a transition element salt (e.g., a Zn, Zr, and/or Ti salt). In some exemplary embodiments, the permanganate containing composition may include 0.1 g to 60 g of the pennanganate salt (e.g., K, Na, Li, etc.), 0.008 g to 10 g of the transition element salt, and enough water to make 1 L of solution. For example, in some embodiments, the permanganate-containing composition may include 0.375 g to 7.5 g (e.g., 0.375g to 1.5g) of the permanganate salt, 0.02g to 0.04 g of the transition element salt, and enough water to make 1 L of solution.
100441 In some embodiments, the permanganate containing composition may include a permanganate salt (e.g., K, Na, Li, etc.) and an oxidizer (e.g., a 30 wt%
solution of a hydrogen peroxide). In some exemplary embodiments, the permanganate containing composition may include 0.1 g to 60 g of the permanganate salt, 0.08 g to 0.8 g of the oxidizer, and enough water to make I L of solution. For example, in some embodiments, the permanganate containing composition may include 0.375g to 7.5 g (e.g., 0.375g to 1.5g) of the permanganate salt, 0.3 g to 0.5 g of the oxidizer, and enough water to make 1 L of solution.
100451 In some embodiments, the permanganate containing composition may include a permanganate salt (e.g., K, Na, Li, etc.), a transition element salt (e.g., Zn, Zr and/or Ti), and an oxidizer (e.g., a 30 wt% solution of a hydrogen peroxide). In some embodiments, the permanganate containing composition may include 0.1g to g of the permanganate salt, 0.008 g to 10 g of the transition element salt, 0.08 g to 0.8 g of the oxidizer, and enough water to make 1 L of solution. For example, in some embodiments, the permanganate containing composition may include 0.375 g to 7.5 g (e.g., 0.375g, to 1.5g) of the permanganate salt, 0.02 g to 0.04 g of the transition element salt, 0.3 g to 0,5 g of the oxidizer, and enough water to make 1 L of solution.
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10036394262 From: Christine Graff PCT/15S2014/037695 Replacement Sheet [00461 According to some embodiments, the permanganate composition may include an azole compound. ht some embodiments, the permanganate composition may include 0.1 g to 60 g of the permanganate salt (e.g., K, Na, Li, etc.), 0.008 g to 2 g of the azole compound (e.g., 1H-benzotriazole), and enough water to make 1 L
of = solution. For example, in some embodiments, the permanganate composition may include 0.375 g to 7.5 g (e.g., 0.3758 to 1.58) of the permanganate salt, 0.02 g to 0.8 g of the azole compound, and enough water to make 1 L of solution.
[00471 Tn some embodiments, the permanganate composition may include a permanganate salt (e.g., K, Na, Li, etc.), a transition element salt (e.g., Zn, Zr, and/or Ti), and an azole compound (e.g., 1H-benzotriazole). In some embodiments, the permanganate composition may include 0.1 g to 60 g of the permanganate salt, 0.008 g to 10 g of the transition element salt, 0.008 g to 2 g of the azole compound, and enough water to make IL of solution. For example, in some embodiments, the permanganate containing composition may include 0.375 g to 7.5 g (e.g., 0.375g to 1.5g) of the permanganate salt, 0.028 to 0.04 g of the transition element salt, 0.2 g to 0.8 g of the azole compound, and enough water to make 1 L of solution.
[0048) According to some embodiments, the permanganate containing composition may include a rare earth element salt. In some embodiments, the permanganate composition may include 0.1 g to 60 g of the permanganate salt (e.g., K, Ki, Na, etc.), 0.008 g to 10 g of the rare earth element salt (e.g., Ce, Y, Pr, etc.), and enough water to make 1 L of solution. For example, in some embodiments, the permanganate composition may include 0.375g to 7.5 g (e.g., 0.375g to 1.5g) of the permanganate salt, 0.02 g to 0.04 g of the rare earth element salt, and enough water to make 1 L of solution.
Lithium compositions [00491 According to some embodiments of the present invention, a lithium containing composition for application to a metal substrate (e.g., a substrate .
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10036394262 From: Christine Graff PCT/US20144037695 Replacement Sheet comprising aluminum, magnesium, iron, zinc, nickel, and/or an alloy thereof) comprises a lithium source and a carrier.
100501 The lithium source may comprise a lithium salt; a combination of lithium salts, or a combination of a lithium salt with additional Group IA or Group 1 element salts. The Group IA or Group 1 element salt may include any alkali metal (i.e., Group IA or Group 1) cation, such as, for example, Li, Na, K, Rb, Cs and/or Fr. In some embodiments, the alkali metal cation comprises Li, Na, K, Rb and/or Cs. For example, in some embodiments, the alkali metal cation comprises Na, K and/or Mg. Additionally, although the "lithium source" is described here as including a Li ion, Mg may be substituted for all or a part of the Li in the lithium source.
1005111 The lithium salt and/or Group IA or Group 1 clement salts may include any suitable anion capable of forming a salt with the Group IA or Group 1 elements and Mg (e.g., Li, Mg, Na, K, Rb, Cs and/or Fr). Nonlimiting examples of anions suitable for forming a salt with these elements include carbonates, hydroxides, nitrates, halides (e.g., Cr, Br', r or F), sulfates, phosphates and silicates (e.g., orthosilicates and metasilieates). For example, the metal salt may comprise a carbonate, hydroxide, halide, nitrate, sulfate, phosphate and/or silicate (e.g., orthosilicate or mctasilicate) of Li, Na, K, Rb, Cs, Fr and/or Mg. In some embodiments for example, the metal salt may comprise a carbonate, hydroxide, halide, nitrate, sulfate, phosphate and/or silicate (e.g., orthosilicate or metasilicate) of Li, Mg, Na, K, Rb and/or Cs. In some embodiments, for example, the metal salt may comprise a hydroxide, halide and/or phosphate of Li, Na, K, Rb, Cs, Fr and/or Mg.
For example, in some embodiments, the metal salt may comprise a hydroxide, halide and/or phosphate of Li, Na, K and/or Mg. In some embodiments, for example, the metal salt may comprise a hydroxide, halide and/or phosphate of Li, Na and/or K.
[00521 In some embodiments, the concentration of lithium ions in the lithium containing composition may be 0.02 g to 12 g per 1000 g of solution. For example, RECU 13/05/2015 22:01 0041223388270 PST
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10036394262 From: Christine Graff PCT/US2014/037695 Replacement Sheet the lithium concentration in the composition may be 1 g to 2g per 1000g of solution.
Additionally, when other Group IA or Group lions (e.g., sodium and/or potassium ions) are present, the concentration of those ions in the lithium containing composition may be, for example, 0.2 g to 16 g per 1000 g of solution.
[0053] Additionally, in some embodiments, the composition may include at least two metal salts, and the at least two metal salts may comprise different anions and/or cations from each other. For example, the at least two metal salts may comprise different anions but the same cations, or may comprise different cations but the same anions. In some embodiments, for example, the lithium containing composition may include the same cation but at least two different anions. For example, in some embodiments, the lithium containing composition may include a hydroxide ion, and a phosphate and/or halide ion.
[0054] In some exemplary embodiments, the lithium containing composition may include 0.09g to about 16 g hydroxide ions per 1000 g solution. In some embodiments, the lithium containing composition may include 0.2 g to 16 g phosphate ions (e.g., phosphate ions (PO4.3), di-hydrogen phosphate ions (H2PO4), and/or pyrophosphate ions (P2074), or organic phosphates, such as those offered under the name Dequest, available from Monsanto (St. Louis, Mo.)) per 1000 g solution. In some embodiments, the lithium containing composition may include 0.2 g to 1.5 g halide ions (e.g., F ions, which may be present in solution as NaF, for example) per 1000 g solution. In some embodiments, the lithium containing composition may include hydroxide ions and either halide ions or phosphate ions, and in other embodiments, the lithium containing composition may include hydroxide ions, halide ions and phosphate ions. In some embodiments, the lithium containing composition may also include carbonate ions, for example 0.05 g to 12 g carbonate ions per 1000 g of solution, or 1 g to 2 g carbonate ions per 1000 g of solution.
[0055] Additionally, in some embodiments the lithium composition may include Li and another Group IA or Group 1 element, such as, for example, Na. In some RECU 13/05/2015 22:01 0041223388270 PST
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10036394262 From: Christine Graff.
PCPUS2014/037695 Replacement Sheet embodiments, for example, the metal cation is provided in the composition in the form of a metal salt such as a Li salt, a Mg salt, a Na salt, a K salt, a Rb salt and/or a Cs salt In some embodiments, the lithium containing solution is alkaline.
For example, in some embodiments, the lithium containing composition may include a combination of lithium hydroxide and sodium pyrophosphate in an aqueous solution.
100561 Additionally, in some embodiments, the lithium containing composition may include a transition element source. The transition element source may include a transition element, as that term is defined above, and an anion. The anion in the transition element source may be an anion as described above with respect to the metal salts in the permanganate containing composition, or an anion as described above with the respect to the lithium source in the lithium containing composition.
For example, in some embodiments, the transition element source may include zinc, zirconium or the like as the transition element, and phosphate as the anion.
For example, in some embodiments, the lithium containing composition includes 0.1 to 5g per 4 liters (or 0.025 to 1.25 g per 11,), e.g., lg per 4 liters (or 0.25 g per IL), of the transition element source, e.g., Zn phosphate. In some embodiments, for example, embodiments including Zn, the lithium containing composition may include lower amounts of the transition element source, e.g., 0.08 g per IL.
[00571 In some embodiments, the lithium containing composition may be substantially free of transition metals, chromates, other metallates and oxidizing agents. For example in some embodiments, the lithium containing composition may be substantially free of metals other than Group IA or Group 1 metals, and in other embodiments, the lithium containing composition may be substantially free of metals other than Group IA or Group 1 metals and Mg. As used herein, the term "substantially" is used es a term of approximation, and not as a term of degree.
Accordingly, the term "substantially free," as used herein denotes that the amount of the metals (e.g., transition metals) in the composition is negligible, such that if such metals are present in the composition at all, it is as an incidental impurity.
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10036394262 From: Christine Graff PCMJS2014/037695 Replacement Sheet 100581 In some embodiments, the composition may be an aqueous coating composition, and the composition may therefore further include an aqueous carrier which may optionally comprise one or more organic solvents. Nonlimiting examples of suitable such solvents include propylene glycol, ethylene glycol, glycerol, Low molecular weight alcohols, and the like. When used, the organic solvent may be present in the composition in an amount of 1 g to 20 g solvent per liter of composition with the remainder of the carrier being water. For example, in some embodiments, the organic solvent may be present in the composition in an amount of 8.33 g solvent per liter of composition with the remainder of the carrier being water. In some embodiments, for instance, the organic solvent may be present in the composition in an amount of 30 g to 400 g solvent per 12 liters of composition, with the remainder of the carrier being water. For example, in some embodiments, the organic solvent may be present in the composition in an amount of 100 g to 200 8 solvent per 121iters of composition, for example 107 g solvent per 12 liters of composition, with the remainder of the carrier being water. In some embodiments, however, the aqueous carrier is primarily water, e.g., deionized water. The aqueous carrier is provided in an amount sufficient to provide the composition with the concentrations of the metal ions and anions described herein.
100591 The concentration of the lithium source in the composition may be any amount suitable to provide the concentrations of the anions discussed above.
For example, in some embodiments, the concentration of the lithium source in the =
composition may be 0.008 percent by weight up to the solubility limit of the lithium source in the carrier. In some embodiments, for example, the lithium source may be present in the composition in a concentration of! g to 2 g per 1000 g of the composition. In some embodiments, the lithium source may be present in the composition in a concentration of 0.05 g to 12 g per 10008 of the composition.
[OM] In some embodiments of the present invention, the lithium containing composition may further comprise one or more additives for promoting corrosion RECIJ 13/05/2015 22:81 0041223388270 PST
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10036394262 From: Christine Graff PCT/US2014/037695 Replacement Sheet resistance, adhesion to the metal substrate, adhesion of subsequent coatings, and/or to provide another desired aesthetic or functional effect.. An additive, if used, may be present in the composition in an amount of 0.01 weight percent up to 80 weight percent based on the total weight of the composition. For example, in some embodiments, the additive (e.g., a surfactant) may be present in the lithium containing composition at a concentration of 0.015 g to 5 g per 1000 g of solution. In some embodiments, the additive (e.g., a surfactant and/or polyvinylpyrrolidone) may be present in the lithium containing composition at a concentration of 0.15 g to 1 g per 1000 g of solution.
100611 Suitable additives may include a solid or liquid component admixed with the composition for the purpose of affecting one or more properties of the composition. The additive may include, for example, an azole compound (such as those described above with respect to the permanganate containing composition), a surfactant, which can assist in wetting the metal substrate, and/or other additives that can assist in the development of a particular surface property, such as a rough or smooth surface. Other nonlimiting examples of suitable additives include alcohols, co-inhibitors, lithium salts, flow control agents, thixotropic agents such as bentonite clay, gelatins, cellulose, anti-gassing agents, degreasing agents, anti-foaming agents, organic co-solvents, catalysts, dyes, amino acids, urea based compounds, complexing agents, valence stabilizers, and the like, as well as other customary auxiliaries.
Suitable additives are known in the art of formulating compositions for surface coatings and can be used in the compositions according to embodiments of the present.
invention, as would be understood by those of ordinary skill in the art with reference to this disclosure.
[00621 As discussed above, in some embodiments, the lithium containing composition may additionally comprise a surfactant (such as, for example, an anionic, nonionic ancVor cationic surfactant), mixture of surfactants, or detergent-type aqueous solution. Nonlimiting examples of some suitable commercially available smfaciants RECU 13/05/2015 22:01 0041223388270 PST
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10036394262 From: Christine Graff PCT/US2014/037695 Replacement Sheet include Dynol 604 and Carbowet DC-01 (both available from Air Products &
Chemicals, Inc., Allentown, PA), and Triton X-100 (available from The Dow Chemical Company, Midland MI). The surfactant, mixture of surfactants, or detergent-type aqueous solution may be present in the composition in an amount of 0.015 g to 5 g per 1000 g of solution. For example, the surfactant, mixture of surfactants, or detergent-type aqueous solution may be present in the composition in an amount of 0.015 g to 1 g per 1000 g of solution. In one embodiment, the composition having a surfactant, mixture of surfactants, or detergent-type aqueous solution may be utilized to combine a metal substrate cleaning step and a conversion coating step in one process.
10063] As also discussed above, the lithium containing composition may also contain other components and additives such as, but not limited to, carbonates, surfactants, chelators, thickeners, allantoin, polyvinylpyrrolidone, halides, azole compounds (such as those described above, for example, 2,5-dimereapto-1,3,4-thiadiazole) and/or adhesion promoters. For example, in some embodiments, the composition may I.-lather comprise allantoin, polyvinylpyrrolidone, surfactants, and/or other additives and/or co-inhibitors.
[0064] In some embodiments, the lithium containing composition may further include an indicator compound, such as those described above with respect to the permanganate containing compound. The indicator compound may be present in the composition in an amount of from about 0.0001 to 3 g per liter of composition.
For example, in some embodiments, the indicator compound may be present in the composition in an amount of 0.0001 g to 1 g per liter of composition. In some embodiments, for example, the indicator compound may be present in the composition in an amount of 0.082 g to 0.0132 g per liter of composition.
10065] For example, in some embodiments of the present invention, the lithium containing composition may include an aqueous solution including lithium hydroxide (Li0H), lithium di-hydrogen phosphate (Lik-12,04), and a surfactant. In another RECU 13/05/2015 22:01 0041223388270 PST
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10036394262 From: Christine Graff PCT/US2014/037695 Replacement Sheet example embodiments, the lithium containing composition may include an aqueous solution including lithium hydroxide (Li0H), sodium phosphate or pyrophosphate (Na3PO4 or Na4P207), and a surfactant. =
[0066] In yet another example embodiment, the lithium containing composition may include an alkaline aqueous carrier, a lithium ion, another Group IA or Group 1 element ion, a carbonate ion, a hydroxide ion, a phosphate ion, and optionally an additive (e.g., a surfactant, a chelator, a thickener, allantoin, polyvinylpyrrolidone, 2,5-dimereaptor-1,3,4-thiadiazole, a halide (e.g., F), an adhesion promoting silane, and/or an alcohol). For example, in some embodiments, the lithium containing composition may include an aqueous solution including lithium carbonate (Li2CO3), sodium hydroxide (NaOH), sodium phosphate (Na3PO4), a surfactant, and optionally polyvinylpyrrolidone.
[0067] in another example embodiment, the lithium containing composition may include an alkaline aqueous carrier, a lithium ion, a hydroxide ion, a halide ion (e.g., F), and optionally an additive (e.g., a carbonate, a surfactant, a chelator, a thickener, allantoin, polyvinylpyrrolidone, 2,5-dimercaptor-1,3,4-thiadia201e, a halide (e.g., F), an. adhesion promoting silane, and/or an alcohol). For example, in some embodiments, the lithium containing composition may include an aqueous solution including lithium hydroxide (UGH), sodium fluoride (NaF), and a surfactant.
100681 In some embodiments, the lithium containing composition may include 0.05 g to 12 g of LiiCO3, and enough water to make 1 L of composition. For example, in some embodiments, the littutim containing composition may include I g to 2 g of Li2CO3, and enough water to make 1 L of composition.
(oub91 According to some embodiments, the lithium containing composition may include 0.05 g to 12 g Li2CO3, 1g to 20 g ethanol, and enough water to make I
L of composition. For example, in some embodiments, the lithium containing composition may include lg to 2 g ot LI2C01, 8.33 got ethanol, and enough water to make 1 L of composition.
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10036394262 From: Christine Graff PCT/US2014/037695 Replacement Sheet [0070] In some embodiments, the lithium containing composition may include 0.05 g to 12 g of Li2CO3, 0_0001 g to 1 g of an indicator compound, and enough water to make 1 L of composition. For example, in some embodiments, the lithium containing composition may include 1 g to 2 g of Li2CO3, 0.082 g to 0.0132 g of an indicator compound, and enough water to make 1 L of composition.
100711 As discussed above, in some embodiments, the lithium containing composition may be alkaline, i.e., have a pH above 7. For example, in some embodiments, the lithium composition can have a pH above 10, Additionally, in some embodiments, the temperature of the composition, when applied to a substrate, may be 15 C to 120 C, for example 15 C to 25 c (or room temperature).
[0072] The lithium-containing compositions described herein can be used in conjunction with the permanganate-containing compositions to coat metal substrates in order to inhibit corrosion. For example, the metal substrate may first be coated or treated with the permanganate containing compositions, and then coated or treated with the lithium containing compound. Embodiments of methods for coating a metal substrate are described in more detail below.
Substrates [0073] According to another embodiment of the invention, a metal substrate (e.g., an aluminum or aluminum alloy substrate) may comprise a surface that is contacted with the permanganate containing composition and/or the lithium containing composition according to embodiments of the invention. Noialimiting examples of suitable substrates include aluminum, zinc, iron, and/or magnesium substrates.
Additional nonlimiting examples of suitable metal substrates include high copper containing aluminum alloys such as Aluminum 2024.
[0074] According to some embodiments, the metal substrate may he pre-treated prior to contacting the metal substrate with the permanganate-containing composition and/or lithium containing composition described above. As used herein, the term "pre-treating" refers to the surface modification of the substrate prior to subsequent RECU 13/05/2015 22:01 0041223338270 PST
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10036394262 From: Christine Graff PCT/1JS2014/037695 Replacement Sheet processing. Such surface modification can include various operations, including, but not limited to cleaning (to remove impurities and/or dirt from the surface), deoxidizing, and/or application of a solution or coating, as is known in the art. Pre-treatment may have one or more benefits, such as the generation of a more uniform starting metal surface, improved adhesion to a subsequent coating on the pre-treated substrate, and/or modification of the starting surface in such a way as to facilitate the deposition. of a subsequent composition. =
100751 According to some embodiments, the metal substrate may be prepared by first solvent treating the metal substrate prior to contacting the metal substrate with the permanganate containing composition and/or lithium containing composition.
As used herein, the term "solvent treating" refers to rinsing, wiping, spraying, or immersing the substrate in a solvent that assists in the removal of inks, oils, etc. that may be on the metal surface. Alternately, the metal substrate may be prepared by degreasing the metal substrate using conventional degreasing methods prior to contacting the metal substrate with the permanganate containing composition and/or lithium containing composition.
100761 The metal substrate may be pre-treated by solvent treating the metal substrate. Then, the metal substrate may be pre-treated by cleaning the metal substrate with an alkaline cleaner or degreaser. Some nonlimiting examples of suitable alkaline cleaners/degreasers include the "DFM Series" line of products available from PRC-DeSoto International, Inc., Syirrlat, CA. These products are alkaline etching or degreasing agents, and some exemplary products include and DFM10 (both manufactured by PRC-DeSoto International, Inc., Sylmar, CA).
Other nonlimiting examples of suitable degreasing compositions include RECC
and 88X002 (both manufactured by PRC-DeSoto International, Inc., Sylmar, California).
[00771 The metal substrate can optionally be deoxidized after the substrate is degreased. Alternatively, the metal substrate need not be degreased, but may be RECU 13/05/2015 22:01 004122338E270 PST
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Christine Graff PCT/US2014/037695 Replacement Sheet deoxidized before the application of the permanganate-containing composition and/or the lithium containing composition. An exemplary deoxidizing composition can comprise an acid (e.g., nitric acid), a chelator, and a carrier. In one embodiment, the chelator can comprise ascorbic acid. In another embodiment, a phosphoric acid/isopropyl alcohol acidic deoxidizer may be used.
[0078] In some embodiments, a degreaser/deoxidizer composition may include 0.5 g to 5 g of Na011, 0.5 g to 20 g of sodium phosphate, 0.001 g to 5 g of polyvinylpyrrolidone, 0.001 to 5 g of allantoin, 0.05 to 10 g of 142-(ilimethylamino)ethyl)-1 H-tetrazole-5-thiol (DMTZ), 0.01 g to 20 g of Carboweta DC01 Surfactant from Air Products, and enough water to make 1 L of solution.
In another embodiment, a degreaser/deoxidizer composition may include 0.5 to 20 g of potassium hydroxide, 0.05 to 10 g of potassium polyphosphate, 0.5 to 25 g of potassium silicate, 0.5 to 20 g of 1DC01., and enough water to make 1 L of solution. In still another embodiment, a degreaser/deoxidizer composition may include 0.5 to 20 g of sodium hydroxide, 0.05 to 20 g of sodium phosphate, 0.0005 to 5 g of Start Right0 (a water conditioner available from United Pot Group, Inc., Madison, WI), 0.5 to 20 g of CarbowetS DC01 Surfactant from Air Products, and enough water to make 1 L
of solution. According to some embodiments, a degreaser/deoxidizer composition may include 50 to 500 mL of butanol, 50 to 500 mL of isopropanol, 0.01 to 5 inL of phosphoric acid, and enough water to make 1 L of solution. In some embodiments, for example, a degreaserideoxidizer composition may include 0.05 to 5 g of ascorbic acid, 5 to 200 mL of nitric acid, and enough water to make 1 L of solution.
One nonlimiting example of a suitable degreaser/deoxidizer composition is Deft Clean 4000 available from PRC-DeSoto International, Inc., Sylmar, CA.
[0079] in one embodiment, the metal substrate can be treated with an oxide =
farming agent prior to treatment with the permanganate-containing composition and/or lithium containing composition. Exemplary oxide forming agents can comprise lithium and/or aluminum salts. In some embodiments, the oxide RECU 13/05/2015 22:01 0041223388270 PST
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10036394262 From: Christine Graff PCT/US2014/037695 Replacement Sheet forming agent treatment can comprise immersion of the metal substrate in boiling water.
[0080] In some embodiments, the metal substrate may be pre-treated by mechanically deoxidizing the metal prior to applying the composition on the metal substrate. A nonlimiting example of a typical mechanical deoxidizer is uniform roughening of the surface using a Scotch-Brite pad, or similar device.
[0081] According to some embodiments, the metal substrate may be pre-treated by solvent wiping the metal prior to applying the permanganate containing composition and/or the lithium containing composition to the metal substrate.
Nonlirniting examples of suitable solvents include methyl ethyl ketone (MEK), methyl propyl ketone (MPK), acetone, and the like.
[0082] Additional optional procedures for preparing the metal substrate include the use of a surface brightener, such as an acid pickle or light acid etch, or a smut remover.
[0083] The metal substrate may be rinsed with either tap water, or distilled/de-ionized water between each of the pretreatment steps, and may be rinsed well with distilled/de-ionized water and/or alcohol after contact with the permanganate containing composition and/or lithium containing composition according to embodiments of the present invention. However, according to some embodiments of the present invention, some of the above described pm-treatment procedures and rinses may not be necessary prior to or after application of the composition according to embodiments of the present invention. For example, in some embodiments, the metal substrate may be treated with a degreaser and then rinsed. In other embodiments, the metal substrate may be treated with a deoxidizer (e.g., an acidic deoxidizer) and then rinsed. hi still other embodiments, the metal substrate may be treated with a degreaser and then rinsed, and then treated with a deoxidizer and then = rinsed. Additionally, this cleaning process may be performed in one combined process, or may be performed in multiple processes, For example, in some RECU 13/05/2015 22:01 0041223388270 PST
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10036394262 From: Christine Graff PCT/US2014/037695 Replacement Sheet embodiments, the metal substrate may be treated with an alkaline degreaser followed by a rinse, and then followed by treatment with an acidic deoxidizer prior to treatment with the permanganate containing composition and/or lithium containing composition described above.
[0084] According to another embodiment of the present invention, the metal substrate may treated with an acidic deoxidizer comprising an acid ( e . g . , nitric acid) and a metal chelator prior to treatment with the pennanganate-containing composition. An example of the metal chelator is Vitamin C. In some =
embodiments, for example, the acidic deoxidizer may include 10 g to 500 g of an acid (e.g., nitric acid), 0.1 g to 15 g of a chelator (e.g., ascorbic acid), and enough water to make 1 I. of solution. For example, in some embodiments, the acidic deoxidizer may include 70 g to 200 g of an acid, 0.5 g to 3g of a chelator, and enough water to make 1 L of solution.
[0085] Once the metal substrate has been appropriately pretreated, if desired, the permanganate containing composition according to embodiments of the present invention may then be allowed to come in contact with at least a portion of the surface of the metal substrate, The metal substrate may be contacted with the composition using any conventional technique, such as dip immersion, spraying, or spreading using a brush, roller, or the like. With regard to application via spraying, =
conventional (automatic or manual) spray techniques and equipment used for air spraying may be used. In other embodiments, the composition may he applied using an electrolytic-coating system.
[0086j After contacting the metal substrate with the permanganate containing composition, the metal substrate may optionally be air dried. However, the substrate need not be dried, and in some embodiments, drying is omitted. A. rinse is also not = required, but may be performed if desired.
100871 According to some embodiments, the metal substrate may be first prepared by mechanical abrasion and then wet-wiped to remove smut. The substrate may then RECU 13/05/2015 22:01 0041223388270 PST
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10036394262 From Christine Graff PCT/US2014/037695 Replacement Sheet optionally be air-dried prior to application. However, the substrate need not be dried, and in some embodiments, drying is omitted. Next, the permanganate containing composition may be applied to the metal substrate and optionally allowed to dry, for example in the absence of heat greater than room temperature. However, drying is not required, and in some embodiments, drying is omitted_ The substrate need not be rinsed, and the metal substrate may then be further coated with the lithium containing compositions described above, conversion coatings, primers and/or top coats to achieve a substrate with a finished coating.
[0088J When the composition is applied to the metal substrate by immersion, the immersion times may vary from a few seconds to multiple hours, for example less than 30 minutes or three minutes or less. In some embodiments, for example, the immersion time may he 2 to 10 minutes or 2 to 5 minutes. When the composition is applied to the metal substrate using a spray application, the composition may be brought into contact with at least a portion of the substrate using conventional spray application methods. The dwell time in which the composition remains in contact with the metal substrate may vary from a few seconds to multiple hours, for example less than 30 minutes or three minutes or less. For example, in some embodiments, the dwell time may be 2 to 10 minutes or 2 to 5 minutes. As discussed above, the permanganate containing composition may have a pH of 2 to 14, for example 4 to 10.
[0089] The permanganate containing compositions may also be applied using other techniques known in the art, such as application via swabbing. Again, the dwell time in which the composition remains in contact with the metal substrate may vary from a few seconds to multiple hours, for example less than 30 minutes or three minutes or less. For example, in some embodiments, the dwell time may be 2 to minutes or 2 to 5 minutes.
[0090] After contacting the metal substrate with the permanganate containing composition, the metal substrate may optionally be air dried, and then rinsed with tap water, or distilled/de-ionized water. Alternately, after contacting the metal substrate RECU 13/05/2015 22:01 0041223383270 PST
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10036394262 From: Christine Graff PCT/US2014/037695 Replacement Sheet with the permanganate containing composition, the metal substrate may be rinsed with tap water, or distilled/de-ionized water, and then subsequently air dried (if desired). However, the substrate need not be dried, and in some embodiments, drying is omitted. Additionally, as noted above, the substrate need not be rinsed, and the metal substrate may then be further coated with the lithium containing composition described above, conversion coatings, primers and/or top coats to achieve a substrate with a finished coating. Accordingly, in some embodiments this subsequent rinse may be omitted.
[0091] In some embodiments, the permanganate containing composition according to embodiments of the invention may be applied to the metal substrate for I
to 10 minutes (for example, 2 to 5 minutes), and the surface of the metal substrate may be kept wet by reapplying the composition. Then, the composition is optionally allowed to dry, for example in the absence of heat greater than room temperature, for to 10 minutes (for example, 7 minutes) after the last application of the composition.
However, the substrate does not need to be allowed to thy, and in some embodiments, drying is omitted. For example, according to some embodiments, a solvent (e.g., alcohol) may be used to rinse the substrate, which allows the omission of a drying step. Alternatively, the metal substrate may be rinsed with deionized water (e.g., for 2 minutes) and optionally allowed to dry.
=
[00921 After the drying step (if performed), the metal substrate may be contacted with the lithium containing composition described above for 2 to 10 minutes, for example 2 to 3 minutes. In some embodiments, for example, the lithium composition includes the lithium source, the carrier, and an azole compound. By treating the metal substrate first with a permanganate-containing composition, followed by application of the lithium containing composition including an azole compound, the result is a favorable reaction on the substrate of the metal permanganate treated substrate. The lithium containing composition may then be dried on the substrate (if desired), or can optionally be rinsed from the substrate.
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10036394262 From: Christine Graff =
PCT/US2014/037695 Replacement Sheet =
[0093] After the drying step (if performed) after application of the lithium containing composition, the metal substrate may be coated with a conversion coating, e.g., a rare earth conversion coating, such as a cerium or yttrium based conversion coating. Examples of such coatings include those having cerium and/or yttrium salts.
In addition to rare earth coatings, any suitable conversion coating chemistry may be used, such as, for example, those that are capable of forming a precipitate upon a change in pH. Nonlimiting examples of such coating chemistries include trivalent chrome, such as Alodine 5900 (available from Henkel Technologies, Madison Heights, MI), zirconium, such as Alodine 5900 (available from Henkel Technologies, Madison Heights, MI), sol gel coatings, such as those sold under the name DesoGerrm (available from PRC-DeSoto International, Inc. of Sylmar, CA), cobalt coatings, vanadate coatings, molybdate coatings, permanganate coatings, and the like, as well as combinations, such as, but not limited to Y and Zr. The conversion coating (e.g., a rare earth conversion coating) may be applied to the metal substrate for 5 minutes.
The substrate need not be rinsed, and the metal substrate may then be further coated with primers and/or top coats to achieve a substrate with a finished coating.
[0094] According to some embodiments, a method of treating a substrate includes cleaning the substrate by applying a cleaning composition to the substrate.
The cleaning composition may be either acidic or alkaline. In some embodiments, for example, cleaning the substrate may include applying an acidic cleaning composition to the substrate, and/or applying an alkaline cleaning composition to the substrate.
The acidic cleaning composition may include, for example, an acidic deoxidizer, such as those described above. Additionally, the alkaline cleaning composition may include, for example, an alkaline degreaser, such as those described above.
The acidic and/or alkaline cleaning composition may be applied to the substrate for the times and under the conditions described above with respect to the deoxidizers and degreasers.
[0095] The method may further include rinsing the substrate after cleaning with the acidic composition and/or the alkaline composition. A single rinse may be RECU 13/05/2015 22:01 0041223388270 PST
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10036394262 From: Christine Graff PCMS2014/037695 Replacement Sheet performed, or multiple rinses may be performed. For example, in some embodiments, two rinses may be performed. Each rinse may include, for example, a rinse with deionized water.
[0096J Additionally, the method may include applying a first composition comprising a permanganate source and a first carrier to the cleaned substrate.
The = first composition may include the permanganate source and carrier in the amounts and concentrations discussed above with respect to the permanganate containing composition. Also, the first composition may include the permanganate compositions described above. However, the first composition need not include all the components described above with respect to the penaianganate containing composition. For example, in some embodiments, the first composition includes the permanganate source and the carrier, but does riot include an additional metal salt as a corrosion inhibitor. Indeed, in some embodiments, the first composition "consists of' or "consists essentially of' the permanganate source and the carrier. As used herein, the term "consists of " is used to exclude all unlisted components except for normal, or naturally occurring impurities, and the term "consists essentially of' is used to exclude all unlisted components that do not materially affect the performance of the first composition. For example, in some embodiments, the term "consists essentially of' in connection with the first composition excludes components such as additional metal salts (i.e., other than the permanganate source), azote compounds, and other additives. The first composition may be applied to the substrate for the times and under the conditions described above with respect to the permanganate containing composition.
10097] The method may also include rinsing the substrate after application of the first composition. A single rinse may be performed, or multiple rinses may be performed. For example, in some embodiments, two rinses may be performed. Each rinse may include, for example, a rinse with deionized water.
[00911] In addition, the method may include applying a second composition comprising a lithium source and a second carrier to the permanganate treated RECU 13/ 05/2015 22:01. 0041223388270 PST
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10036394262 From: Christine Graff PCT/US2014/037695 Replacement Sheet substrate. The second composition may include the lithium source and the second can-ier in the amounts and concentrations discussed above with respect to the lithium containing composition. Also, the second composition may include the lithium containing compositions described above. For example, in some embodiments, the second composition may include the lithium source, the second carrier, and an indicator compound (e.g., catechol violet) and/or an azole compound (e.g., 2,5-. dimcrcapto- I ,3,4-thiadiazole, 111-benzoniazole, IH-1,2,3-triazole, 2-am ino-5-mercapto-1,3,4-thiadiazo I e, and/or 2-amino-1,3,4-thiadiazole). When included in the second composition, the indicator compound and/or azole compound may be present in the amounts and concentrations described above with respect to those components in the lithium containing composition.
[0099] The following examples are presented for illustrative purposes only and do not limit the scope of the present invention.
Example I - Permanganate Containing Composition [001001 A solution (Soln 0) was prepared by mixing 4.5 g of potassium permanganate (1C.Mn04) in enough dcionized water to make 12 liters.
Example 2 - Pemumganate Containing Composition 1001011 A solution (Soln 1) was prepared by mixing 4.5 g of potassium permanganate (1(Mn04) and 0.5 g of cerium nitrate (Ce(N01)3) in enough deionized water to make 12 liters.
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10036394262 From. Christine Graff PCT/US2014/037695 Replacement Sheet Example 3 - Permanggimte Containing Composition [001021 A solution (Soln 2) was prepared by mixing 4.5 g of potassium = permanganate (KIVIn04) and 0.5 g of 1H-benzotriazole (BTA) in enough deionized water to make 12 liters.
Example 4- Permanganate Containing Composition [00103] A solution (Soln 3) was prepared by mixing 4.5 g of potassium permanganate (KMn04) and 0.5 g of hydrogen peroxide (11202) in enough deionized water to make 12 liters.
Example 5 - Permanganate ContainingõComposition [00104] A solution (Sohn 4) was prepared by mixing 30 g ofputassium permanganate (KM.n04) in enough deionized water to make 12 liters.
Example 6 - Lithium Containing Composition [00105] A solution (SIB) was prepared by mixing 12 g of lithium carbonate (Li2CO3) in enough deionized water to make 12 liters.
Example 7- Lithium. Containing Composition [00106J A solution (SIB-CV) was prepared by mixing 4.5 g of lithium carbonate (Li2CO3), and 0.158 g of catechol violet in enough deionized water to make 12 liters.
Example 8 - Lithium Containing Composition [00107] A solution (SIC) was prepared by mixing 18.4 g of lithium carbonate (Li2CO3) in enough deionized water to make 12 liters.
Example 9 - Lithium Containing Composition 1001081 A solution (SIC-BTA) was prepared by mixing 18.4 g of lithium carbonate (Li2CO3), and 1 g of 1H-benzotriazole (BTA) in enough deionized water to make liters.
Example 10 - Lithium Containing Composition [00109] A solution (SIC-CV) was prepared by mixing 18.4 g of lithium carbonate (Li2CO3), and 0.158 g of catechol violet in enough deionized water to make 12 liters.
.
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10036394262 From: Christine Graff PCT/US2014/037695 Replacement Sheet Example 11 - Lithium Containing Composition [00110] A solution (S2B) was prepared by mixing 12 g of lithium carbonate (L12CO3), and 100 g of ethanol in enough deionized water to make 12 liters.
Example 12 - Lithium Containing Composition [00111] A solution (S2C) was prepared by mixing 18.4 g of lithium carbonate (Li2CO3), and 100 g of ethanol in enough deionized water to make 12 liters.
[00112] The compositions prepared according to Examples 1 through 12 were coated on aluminum panels and tested. In particular, triplicate panels (panels A, B and C) of Bare A12024-T3 (available from Continental Steel & Tube Company, Fort Lauderdale, Florida) were treated in the manner set forth below and shown in the following Table 1. The panels were treated at room temperature, i.e., approximately 25 C. The abbreviations for the compositions in Table I are found in the descriptions of the Examples above.
[00113] First, a de-greaser was applied to the panels for 1.5 minutes. The degreaser used was either DFM 4 (panels 1-4), RECC 1001 (panels 5-8), .
88X002 (panels 9-12 and 21), or DFM 10 (panels 13-20), all of which degreasers are available from PRC-DeSoto International, Inc., Sylmar, CA. After application of the degreaser, each panel was rinsed twice with deionized water for 2 minutes per rinse.
Then, the permanganate- containing composition indicated in the Table (i.e., Soln 0, Soln 1, Soln 2, Soln 3 or Soln 4) or RECC 3070 (a rare earth conversion coating composition available from PRC-DeSoto International, Inc., Sylmar, CA) was applied to each panel for 2 minutes or 5 minutes (as indicated in the Table).
[00114] Each of the panels was then rinsed with deionized water for 2 minutei.
Following the rinse, the lithium-containing composition indicated in the Table (i.e., SIB, SIB-CV, SIC, SIC-BTA, SIC-CV, S2B or S2C) was applied to each of the panels for 2 minutes.
[00115] After treatment, the performance of each of the treated panels was measured by a 4 day neutral salt spray test run in accordance with ASTM B 117.
The test panels were rated according to the ELM Scale, which has the following RECU 13/05/2015 22:01 0041223388270 PST
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10036394262 From: Christine Graff = PCT/US2014/037695 Replacement Sheet rating parameters:
Substantially identical to how it went into test 9 Passes MIL-C-554I with less than or equal to 3 pits (with or without tails) per 3" x 6" panel 8 Passes MIL-C-5541 with less than or equal to 3 pits with white corrosion tails (Discoloring tails okay) per 3" x 6 "panel 7 > 3 pits with tails, but not more than 15 pits total 6 > 15 pits total but <40 pits total 5 30% of substrate is corroded 4 50% of substrate is corroded 3 70% of substrate is corroded =-) 85% of substrate is corroded 1 100% of substrate is corroded 100116] The ELM rating for each panel, reported as an average rating of the triplicate panels (A-C) for each listed panel, is shown in Table 2, below.
=
.
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a) to CD
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PCT/US2014/037695 Replacement Sheet a u, 0) I
_______________________________________________________________________________ _____ T APD I I An, ni !NTT
!ELM 4 day =
Panels A-C . ¨ ________________________ Time I App II Rinse Time II !
''''''' ¨ Time HI App - 1 Time IV ¨Pl? ' Time V
1 _ Degrease 'Permanganate Rinse . Lithium 1 salt spray _______________________________________________________________________________ ____ rn _ c-) c 1 DFM4 3,5m Rinsex2 lin Soln 0 2m Rinse 2m SIC 2m I 9 !-.
-.._ oo 2 DFM4 3.5m Rinsex2 2m Soln 1 2m Rinse 2m SIC 2m 10 cn ---.
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r __________________________ _ _________________ -' ,! 'E-Y', 3 DFIVI4 3.5m Rinsex2 I 2ni Soln 2 2m Rinse 2m SIC 2m 8 c"
1_ _______________________________________________________________________________ _____________________ , ND
La ^ I-. La 4 1)FM4 3.5m Rinsex2 2m Soln 3 2m Rinse 2m SIC 2m 9 P?
1, RECC I
I 3.5m Rinsex2 2m Soln 0 2m Rinse 2m SIC
2m 9 in N3 j 0 IQ r ¨I OJ L, CO
RECC
co 6 3.5m ' Rinsex2 2m Soln 1 2m Rinse 2m SIC 2m 9 co KJ
al RECC
7 3.5m Rinse x2 2m Soln 2 2m Rinse 2m SIC 2m 8 RECC
8 3.5m Rinsex2 ",rn. Soln 3 "Im Rinse 2m SIC 2m 9 -o _______________________________________________________________________________ ______________ oi : ! ______________________________ _______________________________________________________________________________ ______ _ o co a) (,) CO
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App V Time v ELM4IsLay.
Panels A-C Time I App 11 Rinse Time ________ n 1Permõganatel Time lli Rinse Tiiite Y Lithi Degrease salt spray 9 8SX002 3.5m Rinse x2 2m Soln 0 2m Rinse 2m SIC 2m 8 _ rri3 88X002 ! 3.5m Rinse x2 2m &An 1 2m Rinse 2m SIC 2m 8 o c , _______________________________________________________________________________ ___________________ co --...
11 88X002 ! 3.5m Rinse x2 2m So ln 2 2m Rinse 2m1 SIC 2m 8 cm in -,..
.
..... iv 12 88X002 3.5m Rinse x2 2m Soln 3 2m Rinse 2m SIC 2m 1 8 2 0' .
9' = = ^, ' 13 IDPMIO 3.5m Rinse x2 [ 2m Soln 0 2m Rinse 2m SIC 2in 9 a 14 I DMA 10 3.5m Rinse x2 2m Soln 1 2m Rinse 2m SIC 2m 9 ¨1W
co DFM 10 3.5m Rinse x2 2m Soln 2 2m Rinse 2m SIC
2m 8 co co 1.3 ¨, rs) 16 rom 1 c) 3.5m Rinse x2 2m Soln 3 2rn Rinse 2m SIC 2m 9 17 DFM 10 3.5m Rinse x2 2m 3070 5m Rinse 2m SIC 2m 9
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10036394262 From: Christine Graff PCT/US2014/037695 Replacement Sheet orange, xylenol orange, catechol violet, bromophenol blue, green and purple, eriochrome black T, Celestine blue, hematoxylin, calmagite, gallocyanine, and combinations thereof. According to some embodiments, the indicator compound comprises an organic indicator compound that is a metal ion indicator.
Nonlimiting examples of indicator compounds include those found in Table 1. Fluorescent indicators, which will emit light in certain conditions, can also be used according to the present invention, although in certain embodiments the use of a fluorescent indicator is specifically excluded. That is, in certain embodiments, conjugated compounds that exhibit fluorescence are specifically excluded. As used herein, "fluorescent indicator" and like terms refer to compounds, molecules, pigments, and/or dyes that will fluoresce or otherwise exhibit color upon exposure to ultraviolet or visible light. To "fluoresce" will be understood as emitting light following absorption of light or other electromagnetic radiation_ Examples of such indicators, often referred to as "tags," include acridine, anthraquinone, coumarin, diphenylraethane, diphenylnaphthlymethane, quinoline, stilbene, triphenylmethane, anthmeine and/or molecules containing any of these moieties and/or derivatives of any of these such as rhodamines, phenanthridincs, oxazines, fluorones, cyanines and/or acridines.
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10036394262 From: Christine Graff PCTTUS2014/037695 Replacement Sheet TABLE I
CAS keg.
Compound Structure No.
Catechol Violet 115-41-3 . 0 Synonyms: OH , Catecholsullimphthalein; I
0=S=0 Pyrocatecholsulfonephthalein; HO
, Pyrocatechol Violet HO
Xylenol Orange o" 3618-43-7 Synonym: 0y0H
bis(carboxymethyl)aminomethyn- OHY
o-cresolsulfonephthalein tetrasodium salt Ho r,N,,A0H
[0036] According to one embodiment, the conjugated compound comprises catechol violet, as shown in Table I. Cateclaol violet (CV) is a sulfone phthalein dye made from condensing two moles of pyrocatechol with one mole of o-sulfobenzoic acid anhydride. It has been found that CV has indicator properties and when incorporated into corrosion resistant compositions having metal ions, it forms complexes, making it useful as a chelotnetric reagent. As the composition containing the CV chelates metal ions, a generally blue to blue-violet color is observed.
.
100371 According to another embodiment, xylenol orange, as shown in Table 1 is employed in the compositions according to embodiments of the present invention. It has been found that xylcnol orange has metal ion indicator properties and when incorporated into corrosion resistant compositions having metal ions, it forms complexes, making it useful as a chelometric reagent. As the composition containing the xylenol orange chelates metal ions, a solution of xylenol orange turns from red to a generally blue color.
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10036394262 From. Christine Graff PCT/US2014/037695 Replacement Sheet 100381 The indicator compound may be present in the composition in an amount of 0.01g/1000 g solution to 3 g/1000 g solution, such as 0.05g/1000 g solution to 0.1 g/1000 g solution.
100391 In some embodiments of the present invention, the conjugated compound, if it changes color in response to a certain external stimulus, provides a benefit when using the current compositions, in that it can serve as a visual indication that a substrate has been treated with the composition. For example, a composition comprising an indicator that changes color when exposed to a metal ion that is present in the substrate will change color upon complexing with metal ions in that substrate;
this allows the user to see that the substrate has been contacted with the composition.
Similar benefits can be realized by depositing an alkaline or acid layer on a substrate and contacting the substrate with a composition of the present invention that changes color when exposed to an alkaline or acidic pH.
[0040] In addition, the use of certain conjugated compounds according to embodiments of the present invention can provide the substrate with improved adhesion to subsequently applied coating layers. This is particularly true it' the conjugated compound has hydroxyl functionality. Accordingly, some embodiments of the present compositions allow for deposition of subsequent coating layers onto a substrate treated according to embodiments of the present invention without the need for a primer layer. Such coating layers can include urethane coatings and epoxy coatings.
[00411 The permanganate containing composition may have an alkaline, neutral or acidic pH. For example, in some embodiments, the permanganate containing composition may have a pH of 2 to 14. In some embodiments, for example, the permanganate composition may have a pH of 4 to 10.
[00421 In some embodiments, the permanganate containing composition may include 0.1 g to 60 g of a permanganate salt (e.g., K, Li, Na, etc.) and enough water to make 1 L of solution. According to some embodiments, for example, the RECU 13/05/2015 22:01 0041223388270 PST
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10036394262 From: Christine Graff PCT/US2014/037695 Replacement Sheet permanganate composition may include 0.375 g to 7.5 g (e.g., 0.375g to 2.5g) of the permanganate salt, and enough water to make 1 L of solution.
100431 In other embodiments, the permanganate containing composition may further include a transition element salt (e.g., a Zn, Zr, and/or Ti salt). In some exemplary embodiments, the permanganate containing composition may include 0.1 g to 60 g of the pennanganate salt (e.g., K, Na, Li, etc.), 0.008 g to 10 g of the transition element salt, and enough water to make 1 L of solution. For example, in some embodiments, the permanganate-containing composition may include 0.375 g to 7.5 g (e.g., 0.375g to 1.5g) of the permanganate salt, 0.02g to 0.04 g of the transition element salt, and enough water to make 1 L of solution.
100441 In some embodiments, the permanganate containing composition may include a permanganate salt (e.g., K, Na, Li, etc.) and an oxidizer (e.g., a 30 wt%
solution of a hydrogen peroxide). In some exemplary embodiments, the permanganate containing composition may include 0.1 g to 60 g of the permanganate salt, 0.08 g to 0.8 g of the oxidizer, and enough water to make I L of solution. For example, in some embodiments, the permanganate containing composition may include 0.375g to 7.5 g (e.g., 0.375g to 1.5g) of the permanganate salt, 0.3 g to 0.5 g of the oxidizer, and enough water to make 1 L of solution.
100451 In some embodiments, the permanganate containing composition may include a permanganate salt (e.g., K, Na, Li, etc.), a transition element salt (e.g., Zn, Zr and/or Ti), and an oxidizer (e.g., a 30 wt% solution of a hydrogen peroxide). In some embodiments, the permanganate containing composition may include 0.1g to g of the permanganate salt, 0.008 g to 10 g of the transition element salt, 0.08 g to 0.8 g of the oxidizer, and enough water to make 1 L of solution. For example, in some embodiments, the permanganate containing composition may include 0.375 g to 7.5 g (e.g., 0.375g, to 1.5g) of the permanganate salt, 0.02 g to 0.04 g of the transition element salt, 0.3 g to 0,5 g of the oxidizer, and enough water to make 1 L of solution.
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10036394262 From: Christine Graff PCT/15S2014/037695 Replacement Sheet [00461 According to some embodiments, the permanganate composition may include an azole compound. ht some embodiments, the permanganate composition may include 0.1 g to 60 g of the permanganate salt (e.g., K, Na, Li, etc.), 0.008 g to 2 g of the azole compound (e.g., 1H-benzotriazole), and enough water to make 1 L
of = solution. For example, in some embodiments, the permanganate composition may include 0.375 g to 7.5 g (e.g., 0.3758 to 1.58) of the permanganate salt, 0.02 g to 0.8 g of the azole compound, and enough water to make 1 L of solution.
[00471 Tn some embodiments, the permanganate composition may include a permanganate salt (e.g., K, Na, Li, etc.), a transition element salt (e.g., Zn, Zr, and/or Ti), and an azole compound (e.g., 1H-benzotriazole). In some embodiments, the permanganate composition may include 0.1 g to 60 g of the permanganate salt, 0.008 g to 10 g of the transition element salt, 0.008 g to 2 g of the azole compound, and enough water to make IL of solution. For example, in some embodiments, the permanganate containing composition may include 0.375 g to 7.5 g (e.g., 0.375g to 1.5g) of the permanganate salt, 0.028 to 0.04 g of the transition element salt, 0.2 g to 0.8 g of the azole compound, and enough water to make 1 L of solution.
[0048) According to some embodiments, the permanganate containing composition may include a rare earth element salt. In some embodiments, the permanganate composition may include 0.1 g to 60 g of the permanganate salt (e.g., K, Ki, Na, etc.), 0.008 g to 10 g of the rare earth element salt (e.g., Ce, Y, Pr, etc.), and enough water to make 1 L of solution. For example, in some embodiments, the permanganate composition may include 0.375g to 7.5 g (e.g., 0.375g to 1.5g) of the permanganate salt, 0.02 g to 0.04 g of the rare earth element salt, and enough water to make 1 L of solution.
Lithium compositions [00491 According to some embodiments of the present invention, a lithium containing composition for application to a metal substrate (e.g., a substrate .
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10036394262 From: Christine Graff PCT/US20144037695 Replacement Sheet comprising aluminum, magnesium, iron, zinc, nickel, and/or an alloy thereof) comprises a lithium source and a carrier.
100501 The lithium source may comprise a lithium salt; a combination of lithium salts, or a combination of a lithium salt with additional Group IA or Group 1 element salts. The Group IA or Group 1 element salt may include any alkali metal (i.e., Group IA or Group 1) cation, such as, for example, Li, Na, K, Rb, Cs and/or Fr. In some embodiments, the alkali metal cation comprises Li, Na, K, Rb and/or Cs. For example, in some embodiments, the alkali metal cation comprises Na, K and/or Mg. Additionally, although the "lithium source" is described here as including a Li ion, Mg may be substituted for all or a part of the Li in the lithium source.
1005111 The lithium salt and/or Group IA or Group 1 clement salts may include any suitable anion capable of forming a salt with the Group IA or Group 1 elements and Mg (e.g., Li, Mg, Na, K, Rb, Cs and/or Fr). Nonlimiting examples of anions suitable for forming a salt with these elements include carbonates, hydroxides, nitrates, halides (e.g., Cr, Br', r or F), sulfates, phosphates and silicates (e.g., orthosilicates and metasilieates). For example, the metal salt may comprise a carbonate, hydroxide, halide, nitrate, sulfate, phosphate and/or silicate (e.g., orthosilicate or mctasilicate) of Li, Na, K, Rb, Cs, Fr and/or Mg. In some embodiments for example, the metal salt may comprise a carbonate, hydroxide, halide, nitrate, sulfate, phosphate and/or silicate (e.g., orthosilicate or metasilicate) of Li, Mg, Na, K, Rb and/or Cs. In some embodiments, for example, the metal salt may comprise a hydroxide, halide and/or phosphate of Li, Na, K, Rb, Cs, Fr and/or Mg.
For example, in some embodiments, the metal salt may comprise a hydroxide, halide and/or phosphate of Li, Na, K and/or Mg. In some embodiments, for example, the metal salt may comprise a hydroxide, halide and/or phosphate of Li, Na and/or K.
[00521 In some embodiments, the concentration of lithium ions in the lithium containing composition may be 0.02 g to 12 g per 1000 g of solution. For example, RECU 13/05/2015 22:01 0041223388270 PST
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10036394262 From: Christine Graff PCT/US2014/037695 Replacement Sheet the lithium concentration in the composition may be 1 g to 2g per 1000g of solution.
Additionally, when other Group IA or Group lions (e.g., sodium and/or potassium ions) are present, the concentration of those ions in the lithium containing composition may be, for example, 0.2 g to 16 g per 1000 g of solution.
[0053] Additionally, in some embodiments, the composition may include at least two metal salts, and the at least two metal salts may comprise different anions and/or cations from each other. For example, the at least two metal salts may comprise different anions but the same cations, or may comprise different cations but the same anions. In some embodiments, for example, the lithium containing composition may include the same cation but at least two different anions. For example, in some embodiments, the lithium containing composition may include a hydroxide ion, and a phosphate and/or halide ion.
[0054] In some exemplary embodiments, the lithium containing composition may include 0.09g to about 16 g hydroxide ions per 1000 g solution. In some embodiments, the lithium containing composition may include 0.2 g to 16 g phosphate ions (e.g., phosphate ions (PO4.3), di-hydrogen phosphate ions (H2PO4), and/or pyrophosphate ions (P2074), or organic phosphates, such as those offered under the name Dequest, available from Monsanto (St. Louis, Mo.)) per 1000 g solution. In some embodiments, the lithium containing composition may include 0.2 g to 1.5 g halide ions (e.g., F ions, which may be present in solution as NaF, for example) per 1000 g solution. In some embodiments, the lithium containing composition may include hydroxide ions and either halide ions or phosphate ions, and in other embodiments, the lithium containing composition may include hydroxide ions, halide ions and phosphate ions. In some embodiments, the lithium containing composition may also include carbonate ions, for example 0.05 g to 12 g carbonate ions per 1000 g of solution, or 1 g to 2 g carbonate ions per 1000 g of solution.
[0055] Additionally, in some embodiments the lithium composition may include Li and another Group IA or Group 1 element, such as, for example, Na. In some RECU 13/05/2015 22:01 0041223388270 PST
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10036394262 From: Christine Graff.
PCPUS2014/037695 Replacement Sheet embodiments, for example, the metal cation is provided in the composition in the form of a metal salt such as a Li salt, a Mg salt, a Na salt, a K salt, a Rb salt and/or a Cs salt In some embodiments, the lithium containing solution is alkaline.
For example, in some embodiments, the lithium containing composition may include a combination of lithium hydroxide and sodium pyrophosphate in an aqueous solution.
100561 Additionally, in some embodiments, the lithium containing composition may include a transition element source. The transition element source may include a transition element, as that term is defined above, and an anion. The anion in the transition element source may be an anion as described above with respect to the metal salts in the permanganate containing composition, or an anion as described above with the respect to the lithium source in the lithium containing composition.
For example, in some embodiments, the transition element source may include zinc, zirconium or the like as the transition element, and phosphate as the anion.
For example, in some embodiments, the lithium containing composition includes 0.1 to 5g per 4 liters (or 0.025 to 1.25 g per 11,), e.g., lg per 4 liters (or 0.25 g per IL), of the transition element source, e.g., Zn phosphate. In some embodiments, for example, embodiments including Zn, the lithium containing composition may include lower amounts of the transition element source, e.g., 0.08 g per IL.
[00571 In some embodiments, the lithium containing composition may be substantially free of transition metals, chromates, other metallates and oxidizing agents. For example in some embodiments, the lithium containing composition may be substantially free of metals other than Group IA or Group 1 metals, and in other embodiments, the lithium containing composition may be substantially free of metals other than Group IA or Group 1 metals and Mg. As used herein, the term "substantially" is used es a term of approximation, and not as a term of degree.
Accordingly, the term "substantially free," as used herein denotes that the amount of the metals (e.g., transition metals) in the composition is negligible, such that if such metals are present in the composition at all, it is as an incidental impurity.
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10036394262 From: Christine Graff PCMJS2014/037695 Replacement Sheet 100581 In some embodiments, the composition may be an aqueous coating composition, and the composition may therefore further include an aqueous carrier which may optionally comprise one or more organic solvents. Nonlimiting examples of suitable such solvents include propylene glycol, ethylene glycol, glycerol, Low molecular weight alcohols, and the like. When used, the organic solvent may be present in the composition in an amount of 1 g to 20 g solvent per liter of composition with the remainder of the carrier being water. For example, in some embodiments, the organic solvent may be present in the composition in an amount of 8.33 g solvent per liter of composition with the remainder of the carrier being water. In some embodiments, for instance, the organic solvent may be present in the composition in an amount of 30 g to 400 g solvent per 12 liters of composition, with the remainder of the carrier being water. For example, in some embodiments, the organic solvent may be present in the composition in an amount of 100 g to 200 8 solvent per 121iters of composition, for example 107 g solvent per 12 liters of composition, with the remainder of the carrier being water. In some embodiments, however, the aqueous carrier is primarily water, e.g., deionized water. The aqueous carrier is provided in an amount sufficient to provide the composition with the concentrations of the metal ions and anions described herein.
100591 The concentration of the lithium source in the composition may be any amount suitable to provide the concentrations of the anions discussed above.
For example, in some embodiments, the concentration of the lithium source in the =
composition may be 0.008 percent by weight up to the solubility limit of the lithium source in the carrier. In some embodiments, for example, the lithium source may be present in the composition in a concentration of! g to 2 g per 1000 g of the composition. In some embodiments, the lithium source may be present in the composition in a concentration of 0.05 g to 12 g per 10008 of the composition.
[OM] In some embodiments of the present invention, the lithium containing composition may further comprise one or more additives for promoting corrosion RECIJ 13/05/2015 22:81 0041223388270 PST
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10036394262 From: Christine Graff PCT/US2014/037695 Replacement Sheet resistance, adhesion to the metal substrate, adhesion of subsequent coatings, and/or to provide another desired aesthetic or functional effect.. An additive, if used, may be present in the composition in an amount of 0.01 weight percent up to 80 weight percent based on the total weight of the composition. For example, in some embodiments, the additive (e.g., a surfactant) may be present in the lithium containing composition at a concentration of 0.015 g to 5 g per 1000 g of solution. In some embodiments, the additive (e.g., a surfactant and/or polyvinylpyrrolidone) may be present in the lithium containing composition at a concentration of 0.15 g to 1 g per 1000 g of solution.
100611 Suitable additives may include a solid or liquid component admixed with the composition for the purpose of affecting one or more properties of the composition. The additive may include, for example, an azole compound (such as those described above with respect to the permanganate containing composition), a surfactant, which can assist in wetting the metal substrate, and/or other additives that can assist in the development of a particular surface property, such as a rough or smooth surface. Other nonlimiting examples of suitable additives include alcohols, co-inhibitors, lithium salts, flow control agents, thixotropic agents such as bentonite clay, gelatins, cellulose, anti-gassing agents, degreasing agents, anti-foaming agents, organic co-solvents, catalysts, dyes, amino acids, urea based compounds, complexing agents, valence stabilizers, and the like, as well as other customary auxiliaries.
Suitable additives are known in the art of formulating compositions for surface coatings and can be used in the compositions according to embodiments of the present.
invention, as would be understood by those of ordinary skill in the art with reference to this disclosure.
[00621 As discussed above, in some embodiments, the lithium containing composition may additionally comprise a surfactant (such as, for example, an anionic, nonionic ancVor cationic surfactant), mixture of surfactants, or detergent-type aqueous solution. Nonlimiting examples of some suitable commercially available smfaciants RECU 13/05/2015 22:01 0041223388270 PST
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10036394262 From: Christine Graff PCT/US2014/037695 Replacement Sheet include Dynol 604 and Carbowet DC-01 (both available from Air Products &
Chemicals, Inc., Allentown, PA), and Triton X-100 (available from The Dow Chemical Company, Midland MI). The surfactant, mixture of surfactants, or detergent-type aqueous solution may be present in the composition in an amount of 0.015 g to 5 g per 1000 g of solution. For example, the surfactant, mixture of surfactants, or detergent-type aqueous solution may be present in the composition in an amount of 0.015 g to 1 g per 1000 g of solution. In one embodiment, the composition having a surfactant, mixture of surfactants, or detergent-type aqueous solution may be utilized to combine a metal substrate cleaning step and a conversion coating step in one process.
10063] As also discussed above, the lithium containing composition may also contain other components and additives such as, but not limited to, carbonates, surfactants, chelators, thickeners, allantoin, polyvinylpyrrolidone, halides, azole compounds (such as those described above, for example, 2,5-dimereapto-1,3,4-thiadiazole) and/or adhesion promoters. For example, in some embodiments, the composition may I.-lather comprise allantoin, polyvinylpyrrolidone, surfactants, and/or other additives and/or co-inhibitors.
[0064] In some embodiments, the lithium containing composition may further include an indicator compound, such as those described above with respect to the permanganate containing compound. The indicator compound may be present in the composition in an amount of from about 0.0001 to 3 g per liter of composition.
For example, in some embodiments, the indicator compound may be present in the composition in an amount of 0.0001 g to 1 g per liter of composition. In some embodiments, for example, the indicator compound may be present in the composition in an amount of 0.082 g to 0.0132 g per liter of composition.
10065] For example, in some embodiments of the present invention, the lithium containing composition may include an aqueous solution including lithium hydroxide (Li0H), lithium di-hydrogen phosphate (Lik-12,04), and a surfactant. In another RECU 13/05/2015 22:01 0041223388270 PST
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10036394262 From: Christine Graff PCT/US2014/037695 Replacement Sheet example embodiments, the lithium containing composition may include an aqueous solution including lithium hydroxide (Li0H), sodium phosphate or pyrophosphate (Na3PO4 or Na4P207), and a surfactant. =
[0066] In yet another example embodiment, the lithium containing composition may include an alkaline aqueous carrier, a lithium ion, another Group IA or Group 1 element ion, a carbonate ion, a hydroxide ion, a phosphate ion, and optionally an additive (e.g., a surfactant, a chelator, a thickener, allantoin, polyvinylpyrrolidone, 2,5-dimereaptor-1,3,4-thiadiazole, a halide (e.g., F), an adhesion promoting silane, and/or an alcohol). For example, in some embodiments, the lithium containing composition may include an aqueous solution including lithium carbonate (Li2CO3), sodium hydroxide (NaOH), sodium phosphate (Na3PO4), a surfactant, and optionally polyvinylpyrrolidone.
[0067] in another example embodiment, the lithium containing composition may include an alkaline aqueous carrier, a lithium ion, a hydroxide ion, a halide ion (e.g., F), and optionally an additive (e.g., a carbonate, a surfactant, a chelator, a thickener, allantoin, polyvinylpyrrolidone, 2,5-dimercaptor-1,3,4-thiadia201e, a halide (e.g., F), an. adhesion promoting silane, and/or an alcohol). For example, in some embodiments, the lithium containing composition may include an aqueous solution including lithium hydroxide (UGH), sodium fluoride (NaF), and a surfactant.
100681 In some embodiments, the lithium containing composition may include 0.05 g to 12 g of LiiCO3, and enough water to make 1 L of composition. For example, in some embodiments, the littutim containing composition may include I g to 2 g of Li2CO3, and enough water to make 1 L of composition.
(oub91 According to some embodiments, the lithium containing composition may include 0.05 g to 12 g Li2CO3, 1g to 20 g ethanol, and enough water to make I
L of composition. For example, in some embodiments, the lithium containing composition may include lg to 2 g ot LI2C01, 8.33 got ethanol, and enough water to make 1 L of composition.
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10036394262 From: Christine Graff PCT/US2014/037695 Replacement Sheet [0070] In some embodiments, the lithium containing composition may include 0.05 g to 12 g of Li2CO3, 0_0001 g to 1 g of an indicator compound, and enough water to make 1 L of composition. For example, in some embodiments, the lithium containing composition may include 1 g to 2 g of Li2CO3, 0.082 g to 0.0132 g of an indicator compound, and enough water to make 1 L of composition.
100711 As discussed above, in some embodiments, the lithium containing composition may be alkaline, i.e., have a pH above 7. For example, in some embodiments, the lithium composition can have a pH above 10, Additionally, in some embodiments, the temperature of the composition, when applied to a substrate, may be 15 C to 120 C, for example 15 C to 25 c (or room temperature).
[0072] The lithium-containing compositions described herein can be used in conjunction with the permanganate-containing compositions to coat metal substrates in order to inhibit corrosion. For example, the metal substrate may first be coated or treated with the permanganate containing compositions, and then coated or treated with the lithium containing compound. Embodiments of methods for coating a metal substrate are described in more detail below.
Substrates [0073] According to another embodiment of the invention, a metal substrate (e.g., an aluminum or aluminum alloy substrate) may comprise a surface that is contacted with the permanganate containing composition and/or the lithium containing composition according to embodiments of the invention. Noialimiting examples of suitable substrates include aluminum, zinc, iron, and/or magnesium substrates.
Additional nonlimiting examples of suitable metal substrates include high copper containing aluminum alloys such as Aluminum 2024.
[0074] According to some embodiments, the metal substrate may he pre-treated prior to contacting the metal substrate with the permanganate-containing composition and/or lithium containing composition described above. As used herein, the term "pre-treating" refers to the surface modification of the substrate prior to subsequent RECU 13/05/2015 22:01 0041223338270 PST
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10036394262 From: Christine Graff PCT/1JS2014/037695 Replacement Sheet processing. Such surface modification can include various operations, including, but not limited to cleaning (to remove impurities and/or dirt from the surface), deoxidizing, and/or application of a solution or coating, as is known in the art. Pre-treatment may have one or more benefits, such as the generation of a more uniform starting metal surface, improved adhesion to a subsequent coating on the pre-treated substrate, and/or modification of the starting surface in such a way as to facilitate the deposition. of a subsequent composition. =
100751 According to some embodiments, the metal substrate may be prepared by first solvent treating the metal substrate prior to contacting the metal substrate with the permanganate containing composition and/or lithium containing composition.
As used herein, the term "solvent treating" refers to rinsing, wiping, spraying, or immersing the substrate in a solvent that assists in the removal of inks, oils, etc. that may be on the metal surface. Alternately, the metal substrate may be prepared by degreasing the metal substrate using conventional degreasing methods prior to contacting the metal substrate with the permanganate containing composition and/or lithium containing composition.
100761 The metal substrate may be pre-treated by solvent treating the metal substrate. Then, the metal substrate may be pre-treated by cleaning the metal substrate with an alkaline cleaner or degreaser. Some nonlimiting examples of suitable alkaline cleaners/degreasers include the "DFM Series" line of products available from PRC-DeSoto International, Inc., Syirrlat, CA. These products are alkaline etching or degreasing agents, and some exemplary products include and DFM10 (both manufactured by PRC-DeSoto International, Inc., Sylmar, CA).
Other nonlimiting examples of suitable degreasing compositions include RECC
and 88X002 (both manufactured by PRC-DeSoto International, Inc., Sylmar, California).
[00771 The metal substrate can optionally be deoxidized after the substrate is degreased. Alternatively, the metal substrate need not be degreased, but may be RECU 13/05/2015 22:01 004122338E270 PST
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Christine Graff PCT/US2014/037695 Replacement Sheet deoxidized before the application of the permanganate-containing composition and/or the lithium containing composition. An exemplary deoxidizing composition can comprise an acid (e.g., nitric acid), a chelator, and a carrier. In one embodiment, the chelator can comprise ascorbic acid. In another embodiment, a phosphoric acid/isopropyl alcohol acidic deoxidizer may be used.
[0078] In some embodiments, a degreaser/deoxidizer composition may include 0.5 g to 5 g of Na011, 0.5 g to 20 g of sodium phosphate, 0.001 g to 5 g of polyvinylpyrrolidone, 0.001 to 5 g of allantoin, 0.05 to 10 g of 142-(ilimethylamino)ethyl)-1 H-tetrazole-5-thiol (DMTZ), 0.01 g to 20 g of Carboweta DC01 Surfactant from Air Products, and enough water to make 1 L of solution.
In another embodiment, a degreaser/deoxidizer composition may include 0.5 to 20 g of potassium hydroxide, 0.05 to 10 g of potassium polyphosphate, 0.5 to 25 g of potassium silicate, 0.5 to 20 g of 1DC01., and enough water to make 1 L of solution. In still another embodiment, a degreaser/deoxidizer composition may include 0.5 to 20 g of sodium hydroxide, 0.05 to 20 g of sodium phosphate, 0.0005 to 5 g of Start Right0 (a water conditioner available from United Pot Group, Inc., Madison, WI), 0.5 to 20 g of CarbowetS DC01 Surfactant from Air Products, and enough water to make 1 L
of solution. According to some embodiments, a degreaser/deoxidizer composition may include 50 to 500 mL of butanol, 50 to 500 mL of isopropanol, 0.01 to 5 inL of phosphoric acid, and enough water to make 1 L of solution. In some embodiments, for example, a degreaserideoxidizer composition may include 0.05 to 5 g of ascorbic acid, 5 to 200 mL of nitric acid, and enough water to make 1 L of solution.
One nonlimiting example of a suitable degreaser/deoxidizer composition is Deft Clean 4000 available from PRC-DeSoto International, Inc., Sylmar, CA.
[0079] in one embodiment, the metal substrate can be treated with an oxide =
farming agent prior to treatment with the permanganate-containing composition and/or lithium containing composition. Exemplary oxide forming agents can comprise lithium and/or aluminum salts. In some embodiments, the oxide RECU 13/05/2015 22:01 0041223388270 PST
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10036394262 From: Christine Graff PCT/US2014/037695 Replacement Sheet forming agent treatment can comprise immersion of the metal substrate in boiling water.
[0080] In some embodiments, the metal substrate may be pre-treated by mechanically deoxidizing the metal prior to applying the composition on the metal substrate. A nonlimiting example of a typical mechanical deoxidizer is uniform roughening of the surface using a Scotch-Brite pad, or similar device.
[0081] According to some embodiments, the metal substrate may be pre-treated by solvent wiping the metal prior to applying the permanganate containing composition and/or the lithium containing composition to the metal substrate.
Nonlirniting examples of suitable solvents include methyl ethyl ketone (MEK), methyl propyl ketone (MPK), acetone, and the like.
[0082] Additional optional procedures for preparing the metal substrate include the use of a surface brightener, such as an acid pickle or light acid etch, or a smut remover.
[0083] The metal substrate may be rinsed with either tap water, or distilled/de-ionized water between each of the pretreatment steps, and may be rinsed well with distilled/de-ionized water and/or alcohol after contact with the permanganate containing composition and/or lithium containing composition according to embodiments of the present invention. However, according to some embodiments of the present invention, some of the above described pm-treatment procedures and rinses may not be necessary prior to or after application of the composition according to embodiments of the present invention. For example, in some embodiments, the metal substrate may be treated with a degreaser and then rinsed. In other embodiments, the metal substrate may be treated with a deoxidizer (e.g., an acidic deoxidizer) and then rinsed. hi still other embodiments, the metal substrate may be treated with a degreaser and then rinsed, and then treated with a deoxidizer and then = rinsed. Additionally, this cleaning process may be performed in one combined process, or may be performed in multiple processes, For example, in some RECU 13/05/2015 22:01 0041223388270 PST
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10036394262 From: Christine Graff PCT/US2014/037695 Replacement Sheet embodiments, the metal substrate may be treated with an alkaline degreaser followed by a rinse, and then followed by treatment with an acidic deoxidizer prior to treatment with the permanganate containing composition and/or lithium containing composition described above.
[0084] According to another embodiment of the present invention, the metal substrate may treated with an acidic deoxidizer comprising an acid ( e . g . , nitric acid) and a metal chelator prior to treatment with the pennanganate-containing composition. An example of the metal chelator is Vitamin C. In some =
embodiments, for example, the acidic deoxidizer may include 10 g to 500 g of an acid (e.g., nitric acid), 0.1 g to 15 g of a chelator (e.g., ascorbic acid), and enough water to make 1 I. of solution. For example, in some embodiments, the acidic deoxidizer may include 70 g to 200 g of an acid, 0.5 g to 3g of a chelator, and enough water to make 1 L of solution.
[0085] Once the metal substrate has been appropriately pretreated, if desired, the permanganate containing composition according to embodiments of the present invention may then be allowed to come in contact with at least a portion of the surface of the metal substrate, The metal substrate may be contacted with the composition using any conventional technique, such as dip immersion, spraying, or spreading using a brush, roller, or the like. With regard to application via spraying, =
conventional (automatic or manual) spray techniques and equipment used for air spraying may be used. In other embodiments, the composition may he applied using an electrolytic-coating system.
[0086j After contacting the metal substrate with the permanganate containing composition, the metal substrate may optionally be air dried. However, the substrate need not be dried, and in some embodiments, drying is omitted. A. rinse is also not = required, but may be performed if desired.
100871 According to some embodiments, the metal substrate may be first prepared by mechanical abrasion and then wet-wiped to remove smut. The substrate may then RECU 13/05/2015 22:01 0041223388270 PST
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10036394262 From Christine Graff PCT/US2014/037695 Replacement Sheet optionally be air-dried prior to application. However, the substrate need not be dried, and in some embodiments, drying is omitted. Next, the permanganate containing composition may be applied to the metal substrate and optionally allowed to dry, for example in the absence of heat greater than room temperature. However, drying is not required, and in some embodiments, drying is omitted_ The substrate need not be rinsed, and the metal substrate may then be further coated with the lithium containing compositions described above, conversion coatings, primers and/or top coats to achieve a substrate with a finished coating.
[0088J When the composition is applied to the metal substrate by immersion, the immersion times may vary from a few seconds to multiple hours, for example less than 30 minutes or three minutes or less. In some embodiments, for example, the immersion time may he 2 to 10 minutes or 2 to 5 minutes. When the composition is applied to the metal substrate using a spray application, the composition may be brought into contact with at least a portion of the substrate using conventional spray application methods. The dwell time in which the composition remains in contact with the metal substrate may vary from a few seconds to multiple hours, for example less than 30 minutes or three minutes or less. For example, in some embodiments, the dwell time may be 2 to 10 minutes or 2 to 5 minutes. As discussed above, the permanganate containing composition may have a pH of 2 to 14, for example 4 to 10.
[0089] The permanganate containing compositions may also be applied using other techniques known in the art, such as application via swabbing. Again, the dwell time in which the composition remains in contact with the metal substrate may vary from a few seconds to multiple hours, for example less than 30 minutes or three minutes or less. For example, in some embodiments, the dwell time may be 2 to minutes or 2 to 5 minutes.
[0090] After contacting the metal substrate with the permanganate containing composition, the metal substrate may optionally be air dried, and then rinsed with tap water, or distilled/de-ionized water. Alternately, after contacting the metal substrate RECU 13/05/2015 22:01 0041223383270 PST
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10036394262 From: Christine Graff PCT/US2014/037695 Replacement Sheet with the permanganate containing composition, the metal substrate may be rinsed with tap water, or distilled/de-ionized water, and then subsequently air dried (if desired). However, the substrate need not be dried, and in some embodiments, drying is omitted. Additionally, as noted above, the substrate need not be rinsed, and the metal substrate may then be further coated with the lithium containing composition described above, conversion coatings, primers and/or top coats to achieve a substrate with a finished coating. Accordingly, in some embodiments this subsequent rinse may be omitted.
[0091] In some embodiments, the permanganate containing composition according to embodiments of the invention may be applied to the metal substrate for I
to 10 minutes (for example, 2 to 5 minutes), and the surface of the metal substrate may be kept wet by reapplying the composition. Then, the composition is optionally allowed to dry, for example in the absence of heat greater than room temperature, for to 10 minutes (for example, 7 minutes) after the last application of the composition.
However, the substrate does not need to be allowed to thy, and in some embodiments, drying is omitted. For example, according to some embodiments, a solvent (e.g., alcohol) may be used to rinse the substrate, which allows the omission of a drying step. Alternatively, the metal substrate may be rinsed with deionized water (e.g., for 2 minutes) and optionally allowed to dry.
=
[00921 After the drying step (if performed), the metal substrate may be contacted with the lithium containing composition described above for 2 to 10 minutes, for example 2 to 3 minutes. In some embodiments, for example, the lithium composition includes the lithium source, the carrier, and an azole compound. By treating the metal substrate first with a permanganate-containing composition, followed by application of the lithium containing composition including an azole compound, the result is a favorable reaction on the substrate of the metal permanganate treated substrate. The lithium containing composition may then be dried on the substrate (if desired), or can optionally be rinsed from the substrate.
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10036394262 From: Christine Graff =
PCT/US2014/037695 Replacement Sheet =
[0093] After the drying step (if performed) after application of the lithium containing composition, the metal substrate may be coated with a conversion coating, e.g., a rare earth conversion coating, such as a cerium or yttrium based conversion coating. Examples of such coatings include those having cerium and/or yttrium salts.
In addition to rare earth coatings, any suitable conversion coating chemistry may be used, such as, for example, those that are capable of forming a precipitate upon a change in pH. Nonlimiting examples of such coating chemistries include trivalent chrome, such as Alodine 5900 (available from Henkel Technologies, Madison Heights, MI), zirconium, such as Alodine 5900 (available from Henkel Technologies, Madison Heights, MI), sol gel coatings, such as those sold under the name DesoGerrm (available from PRC-DeSoto International, Inc. of Sylmar, CA), cobalt coatings, vanadate coatings, molybdate coatings, permanganate coatings, and the like, as well as combinations, such as, but not limited to Y and Zr. The conversion coating (e.g., a rare earth conversion coating) may be applied to the metal substrate for 5 minutes.
The substrate need not be rinsed, and the metal substrate may then be further coated with primers and/or top coats to achieve a substrate with a finished coating.
[0094] According to some embodiments, a method of treating a substrate includes cleaning the substrate by applying a cleaning composition to the substrate.
The cleaning composition may be either acidic or alkaline. In some embodiments, for example, cleaning the substrate may include applying an acidic cleaning composition to the substrate, and/or applying an alkaline cleaning composition to the substrate.
The acidic cleaning composition may include, for example, an acidic deoxidizer, such as those described above. Additionally, the alkaline cleaning composition may include, for example, an alkaline degreaser, such as those described above.
The acidic and/or alkaline cleaning composition may be applied to the substrate for the times and under the conditions described above with respect to the deoxidizers and degreasers.
[0095] The method may further include rinsing the substrate after cleaning with the acidic composition and/or the alkaline composition. A single rinse may be RECU 13/05/2015 22:01 0041223388270 PST
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10036394262 From: Christine Graff PCMS2014/037695 Replacement Sheet performed, or multiple rinses may be performed. For example, in some embodiments, two rinses may be performed. Each rinse may include, for example, a rinse with deionized water.
[0096J Additionally, the method may include applying a first composition comprising a permanganate source and a first carrier to the cleaned substrate.
The = first composition may include the permanganate source and carrier in the amounts and concentrations discussed above with respect to the permanganate containing composition. Also, the first composition may include the permanganate compositions described above. However, the first composition need not include all the components described above with respect to the penaianganate containing composition. For example, in some embodiments, the first composition includes the permanganate source and the carrier, but does riot include an additional metal salt as a corrosion inhibitor. Indeed, in some embodiments, the first composition "consists of' or "consists essentially of' the permanganate source and the carrier. As used herein, the term "consists of " is used to exclude all unlisted components except for normal, or naturally occurring impurities, and the term "consists essentially of' is used to exclude all unlisted components that do not materially affect the performance of the first composition. For example, in some embodiments, the term "consists essentially of' in connection with the first composition excludes components such as additional metal salts (i.e., other than the permanganate source), azote compounds, and other additives. The first composition may be applied to the substrate for the times and under the conditions described above with respect to the permanganate containing composition.
10097] The method may also include rinsing the substrate after application of the first composition. A single rinse may be performed, or multiple rinses may be performed. For example, in some embodiments, two rinses may be performed. Each rinse may include, for example, a rinse with deionized water.
[00911] In addition, the method may include applying a second composition comprising a lithium source and a second carrier to the permanganate treated RECU 13/ 05/2015 22:01. 0041223388270 PST
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10036394262 From: Christine Graff PCT/US2014/037695 Replacement Sheet substrate. The second composition may include the lithium source and the second can-ier in the amounts and concentrations discussed above with respect to the lithium containing composition. Also, the second composition may include the lithium containing compositions described above. For example, in some embodiments, the second composition may include the lithium source, the second carrier, and an indicator compound (e.g., catechol violet) and/or an azole compound (e.g., 2,5-. dimcrcapto- I ,3,4-thiadiazole, 111-benzoniazole, IH-1,2,3-triazole, 2-am ino-5-mercapto-1,3,4-thiadiazo I e, and/or 2-amino-1,3,4-thiadiazole). When included in the second composition, the indicator compound and/or azole compound may be present in the amounts and concentrations described above with respect to those components in the lithium containing composition.
[0099] The following examples are presented for illustrative purposes only and do not limit the scope of the present invention.
Example I - Permanganate Containing Composition [001001 A solution (Soln 0) was prepared by mixing 4.5 g of potassium permanganate (1C.Mn04) in enough dcionized water to make 12 liters.
Example 2 - Pemumganate Containing Composition 1001011 A solution (Soln 1) was prepared by mixing 4.5 g of potassium permanganate (1(Mn04) and 0.5 g of cerium nitrate (Ce(N01)3) in enough deionized water to make 12 liters.
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10036394262 From. Christine Graff PCT/US2014/037695 Replacement Sheet Example 3 - Permanggimte Containing Composition [001021 A solution (Soln 2) was prepared by mixing 4.5 g of potassium = permanganate (KIVIn04) and 0.5 g of 1H-benzotriazole (BTA) in enough deionized water to make 12 liters.
Example 4- Permanganate Containing Composition [00103] A solution (Soln 3) was prepared by mixing 4.5 g of potassium permanganate (KMn04) and 0.5 g of hydrogen peroxide (11202) in enough deionized water to make 12 liters.
Example 5 - Permanganate ContainingõComposition [00104] A solution (Sohn 4) was prepared by mixing 30 g ofputassium permanganate (KM.n04) in enough deionized water to make 12 liters.
Example 6 - Lithium Containing Composition [00105] A solution (SIB) was prepared by mixing 12 g of lithium carbonate (Li2CO3) in enough deionized water to make 12 liters.
Example 7- Lithium. Containing Composition [00106J A solution (SIB-CV) was prepared by mixing 4.5 g of lithium carbonate (Li2CO3), and 0.158 g of catechol violet in enough deionized water to make 12 liters.
Example 8 - Lithium Containing Composition [00107] A solution (SIC) was prepared by mixing 18.4 g of lithium carbonate (Li2CO3) in enough deionized water to make 12 liters.
Example 9 - Lithium Containing Composition 1001081 A solution (SIC-BTA) was prepared by mixing 18.4 g of lithium carbonate (Li2CO3), and 1 g of 1H-benzotriazole (BTA) in enough deionized water to make liters.
Example 10 - Lithium Containing Composition [00109] A solution (SIC-CV) was prepared by mixing 18.4 g of lithium carbonate (Li2CO3), and 0.158 g of catechol violet in enough deionized water to make 12 liters.
.
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10036394262 From: Christine Graff PCT/US2014/037695 Replacement Sheet Example 11 - Lithium Containing Composition [00110] A solution (S2B) was prepared by mixing 12 g of lithium carbonate (L12CO3), and 100 g of ethanol in enough deionized water to make 12 liters.
Example 12 - Lithium Containing Composition [00111] A solution (S2C) was prepared by mixing 18.4 g of lithium carbonate (Li2CO3), and 100 g of ethanol in enough deionized water to make 12 liters.
[00112] The compositions prepared according to Examples 1 through 12 were coated on aluminum panels and tested. In particular, triplicate panels (panels A, B and C) of Bare A12024-T3 (available from Continental Steel & Tube Company, Fort Lauderdale, Florida) were treated in the manner set forth below and shown in the following Table 1. The panels were treated at room temperature, i.e., approximately 25 C. The abbreviations for the compositions in Table I are found in the descriptions of the Examples above.
[00113] First, a de-greaser was applied to the panels for 1.5 minutes. The degreaser used was either DFM 4 (panels 1-4), RECC 1001 (panels 5-8), .
88X002 (panels 9-12 and 21), or DFM 10 (panels 13-20), all of which degreasers are available from PRC-DeSoto International, Inc., Sylmar, CA. After application of the degreaser, each panel was rinsed twice with deionized water for 2 minutes per rinse.
Then, the permanganate- containing composition indicated in the Table (i.e., Soln 0, Soln 1, Soln 2, Soln 3 or Soln 4) or RECC 3070 (a rare earth conversion coating composition available from PRC-DeSoto International, Inc., Sylmar, CA) was applied to each panel for 2 minutes or 5 minutes (as indicated in the Table).
[00114] Each of the panels was then rinsed with deionized water for 2 minutei.
Following the rinse, the lithium-containing composition indicated in the Table (i.e., SIB, SIB-CV, SIC, SIC-BTA, SIC-CV, S2B or S2C) was applied to each of the panels for 2 minutes.
[00115] After treatment, the performance of each of the treated panels was measured by a 4 day neutral salt spray test run in accordance with ASTM B 117.
The test panels were rated according to the ELM Scale, which has the following RECU 13/05/2015 22:01 0041223388270 PST
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10036394262 From: Christine Graff = PCT/US2014/037695 Replacement Sheet rating parameters:
Substantially identical to how it went into test 9 Passes MIL-C-554I with less than or equal to 3 pits (with or without tails) per 3" x 6" panel 8 Passes MIL-C-5541 with less than or equal to 3 pits with white corrosion tails (Discoloring tails okay) per 3" x 6 "panel 7 > 3 pits with tails, but not more than 15 pits total 6 > 15 pits total but <40 pits total 5 30% of substrate is corroded 4 50% of substrate is corroded 3 70% of substrate is corroded =-) 85% of substrate is corroded 1 100% of substrate is corroded 100116] The ELM rating for each panel, reported as an average rating of the triplicate panels (A-C) for each listed panel, is shown in Table 2, below.
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2m 8 co co 1.3 ¨, rs) 16 rom 1 c) 3.5m Rinse x2 2m Soln 3 2rn Rinse 2m SIC 2m 9 17 DFM 10 3.5m Rinse x2 2m 3070 5m Rinse 2m SIC 2m 9
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III Time III App IV Time Time IV Ap,p V me V ELM 4 day Degrease Permanganate Rinse Lithium salt spray 19 DFM10 3.5m Rinse x2 2m 3070 5m Rinse 2m SIC-CV 2m 10 (-) 20 DFM10 3.5m Rinse x2 2m 3070 5m Rinse 2m S2C 2m 10 21 88X002 3.5m Rinse x2 2m Soln 4 2m Rinse 2m S2C 2m 10 Ens Nj ,CE
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10036394262 From: Christine Graff PCT/US2014/037695 Replacement Sheet [001171 As can be seen in Table 2, the panels treated with the permanganate and lithium containing compositions according to embodiments of the present invention exhibit good corrosion resistance.
[00118] Additional panels were tested in a manner similar to that described above.
Specifically, triplicate panels (panels A, B and C) of Bare A12024-T3 (available from Continental Steel & Tube Company, Fort Lauderdale, Florida) were treated in the manner set forth below and shown in the following Table 3. The panels were treated at room temperature, i.e., approximately 25 C. The abbreviations for the compositions in Table 3 are found in the descriptions of the Examples above.
[00119] First, a de-greaser was applied to the panels for 3.5 minutes. The degreaser used was either RECC 1001 (panels 22-29), 88X002 (panels 38), or DEM 10 (panels 30-37), all of which degreasers arc available from PRC-DeSoto International, Inc., Sylmar, CA. After application of the degreaser, each panel was rinsed with deionized water for 2 minutes. A deoxidizer composition (i.e., a , solution including 1.25 g of ascorbic acid, 83 niL of nitric acid and enoughtleionized water to make I liter) was then applied to the panels for 2.5 minutes, followed by a 2 minute rinse with deionized water. Then, the permanganate- containing composition according to Example 2 (i.e., Soln 1) wasapplied to each panel for 2-10 minutes (as indicated in the Table), followed by a 2 minute rinse with deionized water. Following the rinse, the lithium-containing composition listed in the Table was applied to each panel for 2-3 minutes (as indicated in the Table).
100129) After treatment, the performance of each of the treated panels was measured by a 4 day neutral salt spray test run in accordance with ASTM B 117.
The test panels were rated according to the ELM Scale, described above. The ELM rating for each panel, reported as an average rating of the triplicate panels (A-C) for each listed panel, is shown in Table 3.
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-..1 (3.5m) (2m) (2.5m) (2m) (2m) BTA m DFMIO Rinse AA Rinse Rinse SIB-33 Solnil 2m 3m 7 (3.5m) (2m) (2.5m) (2m) I (2m) BTA
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DFM10 Rinse AA Rinse Rinse 36 Sola 1 2m S2B 2m 5 (3.5m) (2m) (2.5m) (2m) (2m) c-) DFM10 Rinse AA Rinse Rinse 37 Soln 1 2m S2B 2m 9 (3.5m) (2m) (2.5m) (2m) (2m) Lit 88X002 Rinse AA Rinse Rinse SIB-38 Soln 1 2m 2m 9 CID
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10036394262 From: Christine Graff PCT/US2014/037695 Replacement Sheet 1001211 As can be seen from Table 3, the treatment method may affect the performance of the treated substrate. For example, certain combinations of degreaser or deoxidizer, permanganate solutions, and lithium solutions show enhanced corrosion resistance performance as compared to other combinations.
Additionally, although certain panels (e.g., panels 32 and 33) which were treated in an identical manner may register different ELM ratings, it can be seen that certain of those panels registered reasonably high ELM ratings. This indicates that the application procedure and compositions used on those panels can produce desirable results, and that perhaps there was a flaw or error in the underperforming panel unrelated to the application method or sequence, or the compositions.
(001221 Whereas particular embodiments of the present disclosure have been described above for purposes of illustration, it will be understood by those of ordinary skill in the art that numerous variations of the details of the present disclosure may be made without departing from the invention as defined in the appended claims, and equivalents thereof. For example, although embodiments herein have been described in connection with "a" permanganate, and the like, one or more permanganate or any of the other components recited can be used according to embodiments of the present disclosure.
[001231 Although various embodiments of the present disclosure have been described in terms of "comprising" or "including," embodiments "consisting essentially of' or "consisting of' are also within the scope of the present disclosure.
For example, while the present disclosure describes a composition including a permanganate source and a carrier, a composition and/or a solution consisting essentially of or consisting of the permanganate source and the carrier is also within the scope of the present disclosure. Similarly, although a permanganate source comprising or including a permanganate salt is described, permanganate sources consisting essentially of or consisting al a. permanganate salt are also within the scope of the disclosure. Thus, as described above, the composition may consist essentially of the permanganate source and the carrier. In this context, "consisting essentially of' RECU 13/5/215 22: 01 8E141223388270 PST
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10036394262 From: Christine Graff PCT/US2014/037695 Replacement Sheet means that any additional components in the composition will not materially affect the corrosion resistance of a metal substrate including the composition. For example, a composition consisting essentially of a permanganate source and a carrier is free from anions other than permanganate.
100124] As used herein, unless otherwise expressly specified, all numbers such as those expressing values, ranges, amounts or percentages may be read as if prefaced by the word "about," even if the term does not expressly appear. Further, use of the word "about" reflects the penumbra of variation associated with measurement, significant figures, and interchangeability, all as understood by a person having ordinary skill in the art to which this disclosure pertains. Any numerical range recited herein is intended to include all sub-ranges subsumed therein. Plural encompasses singular and vice versa. For example, while the present disclosure describes "a"
permanganate source, a mixture of such permanganate sources can be used. When ranges are given, any endpoints of those ranges and/or numbers within those ranges can be combined within the scope of the present disclosure. The terms "including" and like terms mean "including but not limited to." Similarly, as used herein, the terms "on,"
"applied on,"
and "formed on" mean on, applied on, or formed on, but not necessarily in contact with the surface. For example, a composition ''applied on" a substrate does not preclude the presence of one or more other coating layers or compositions of the same or different composition located between the applied composition and the substrate.
[00125] Notwithstanding that the numerical ranges and parameters set forth herein may be approximations, numerical values set forth in the specific examples are reported as precisely as is practical. Any numerical value, however, inherently contains certain errors necessarily resulting from the standard variation found in their respective testing measurements. The word "comprising" and variations thereof as used in this description and in the claims do not limit the disclosure to exclude any =
variants or additions.
[ 18 DFM 10 3.5in Rinse x2 2m 3070 5m Rinse 2m BTA 3m 10 0 oi ___________________________________ L_ __________________________________________________________ U3 (0 N) CD
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o g a 4, PCMIS2014/037695 Replacement Sheet 0 I
Panels A-C Apr' _________________ n I Time I App II Rinse Time II APP
III Time III App IV Time Time IV Ap,p V me V ELM 4 day Degrease Permanganate Rinse Lithium salt spray 19 DFM10 3.5m Rinse x2 2m 3070 5m Rinse 2m SIC-CV 2m 10 (-) 20 DFM10 3.5m Rinse x2 2m 3070 5m Rinse 2m S2C 2m 10 21 88X002 3.5m Rinse x2 2m Soln 4 2m Rinse 2m S2C 2m 10 Ens Nj ,CE
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tn a RECU 13/05/2015 22:01 0041223300270 PST
To: Page 48 of 58 2015-05-13 16:03:14 EDT
10036394262 From: Christine Graff PCT/US2014/037695 Replacement Sheet [001171 As can be seen in Table 2, the panels treated with the permanganate and lithium containing compositions according to embodiments of the present invention exhibit good corrosion resistance.
[00118] Additional panels were tested in a manner similar to that described above.
Specifically, triplicate panels (panels A, B and C) of Bare A12024-T3 (available from Continental Steel & Tube Company, Fort Lauderdale, Florida) were treated in the manner set forth below and shown in the following Table 3. The panels were treated at room temperature, i.e., approximately 25 C. The abbreviations for the compositions in Table 3 are found in the descriptions of the Examples above.
[00119] First, a de-greaser was applied to the panels for 3.5 minutes. The degreaser used was either RECC 1001 (panels 22-29), 88X002 (panels 38), or DEM 10 (panels 30-37), all of which degreasers arc available from PRC-DeSoto International, Inc., Sylmar, CA. After application of the degreaser, each panel was rinsed with deionized water for 2 minutes. A deoxidizer composition (i.e., a , solution including 1.25 g of ascorbic acid, 83 niL of nitric acid and enoughtleionized water to make I liter) was then applied to the panels for 2.5 minutes, followed by a 2 minute rinse with deionized water. Then, the permanganate- containing composition according to Example 2 (i.e., Soln 1) wasapplied to each panel for 2-10 minutes (as indicated in the Table), followed by a 2 minute rinse with deionized water. Following the rinse, the lithium-containing composition listed in the Table was applied to each panel for 2-3 minutes (as indicated in the Table).
100129) After treatment, the performance of each of the treated panels was measured by a 4 day neutral salt spray test run in accordance with ASTM B 117.
The test panels were rated according to the ELM Scale, described above. The ELM rating for each panel, reported as an average rating of the triplicate panels (A-C) for each listed panel, is shown in Table 3.
P
II
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CD
(a PCT/US2014/037695 Replacement Sheet a u, co , _____________________________________________________________ -Panels App I ApjL11 App III 6._p IV App V Time App V App 1.7 Time clay A-C Degrease Rinse V V
salt xi spray m C) C
RECC
Rinse AA Rinse Rinse I
22 1001 Sob 1 2m SIB
1 2m 5 cal¨
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'-.., I
t,3 I
N.) 111 R
RECC I
Rinse AA Rinse Rinse 93 1001 Solo 1 lOrn SIB 2m 8 Y1 ND it,' (2m) (2.5m) (2m) (2m) Y1 = = ,.,,' (3.5m) Fi 112 RECC
Rinse AA Rinse Rinse SIB-24 1001 Soln 1 2m 3m (2m) (2.5m) (2m) (2m) BTA
4sni r) (3.5m) ON) La .
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RECC
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CO
Rinse AA Rinse Rinse SIB-r.) 25 1091 Sob 1 10m 3m 7 -a CD
(2m) (2.5m) (2m) (2m) BTA
- (3.5m) RECC
Rinse AA Rinse Rinse SIB-26 1001 Soln 1 2m 2m (2m) (2.5m) (2m) (2m) CV
(3.5m) U) = _, ¨i I
_______________________________________________________________________________ _______________________ 0 La co Cs) CD
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Rinse AA Rinse Rinse SIB-27 1001 SoIn 1 10m 2m 10 (2m) (2.5m) (2m) (2m) CV
(3.5m) RECC
m Rinse AA Rinse Rinse in 18 1 1001 SoInt 2m S2B 2m 6 n c 1 (3.5m) (2m) (2.5m) (2m) (2m) .-..
1 .D.pc,,..., --.
ao I '"-"--- Rinse AA Rinse Rinse LT, 29 1 1001 SoIn I 10m S2B 2m 8 NJ
i (2m) (2.5m) (2m) (2m) I (3.5m) sl 01 .
i _______________________________________________________________________________ ________ T ro N
1 DFM10 Rinse AA Rinse Rinse 9' = = IR', 30 ' Soln 1 2m SIB 2m. 4 ! (3.5m) (2m) (2.5m) (2m) (2m) 9? "
o ' m 1-, ; DFM10 Rinse AA Rinse Rinse 31 I SoIn 1 10m SIB 2m 7 (3.5m) (2m) (2.5m) (2m) (2m) 9O2, LI
w DFMIO Rinse AA Rinse Rinse SIB-co co 32 Soln 1 2m 3m 3 ND
-..1 (3.5m) (2m) (2.5m) (2m) (2m) BTA m DFMIO Rinse AA Rinse Rinse SIB-33 Solnil 2m 3m 7 (3.5m) (2m) (2.5m) (2m) I (2m) BTA
.
_______________________________________________________________________________ _______ -1]
DFIVI10 Rinse AA Rinse Rinse SIB-cr]
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iv NJ
m a g ..
a (D
-a (C2 Ul PCT/US2014/037695 Replacement Sheet u, DFM.10 Rinse AA Rinse Rinse SIB-35 Soln 1 2m 2m 8 (3.5m) (2m) (2.5m) (2m) (2m) CV
DFM10 Rinse AA Rinse Rinse 36 Sola 1 2m S2B 2m 5 (3.5m) (2m) (2.5m) (2m) (2m) c-) DFM10 Rinse AA Rinse Rinse 37 Soln 1 2m S2B 2m 9 (3.5m) (2m) (2.5m) (2m) (2m) Lit 88X002 Rinse AA Rinse Rinse SIB-38 Soln 1 2m 2m 9 CID
(3.5m) (2m) (2.5m) (2m) (2m) B'TA
(51 0 1,3 Z7.) 0 c, L'?
=
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aD
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a RECU 13/05/2015 22:01 0041223386270 PST
To: Page 52 of 58 2015-05-13 16:03:14 EDT
10036394262 From: Christine Graff PCT/US2014/037695 Replacement Sheet 1001211 As can be seen from Table 3, the treatment method may affect the performance of the treated substrate. For example, certain combinations of degreaser or deoxidizer, permanganate solutions, and lithium solutions show enhanced corrosion resistance performance as compared to other combinations.
Additionally, although certain panels (e.g., panels 32 and 33) which were treated in an identical manner may register different ELM ratings, it can be seen that certain of those panels registered reasonably high ELM ratings. This indicates that the application procedure and compositions used on those panels can produce desirable results, and that perhaps there was a flaw or error in the underperforming panel unrelated to the application method or sequence, or the compositions.
(001221 Whereas particular embodiments of the present disclosure have been described above for purposes of illustration, it will be understood by those of ordinary skill in the art that numerous variations of the details of the present disclosure may be made without departing from the invention as defined in the appended claims, and equivalents thereof. For example, although embodiments herein have been described in connection with "a" permanganate, and the like, one or more permanganate or any of the other components recited can be used according to embodiments of the present disclosure.
[001231 Although various embodiments of the present disclosure have been described in terms of "comprising" or "including," embodiments "consisting essentially of' or "consisting of' are also within the scope of the present disclosure.
For example, while the present disclosure describes a composition including a permanganate source and a carrier, a composition and/or a solution consisting essentially of or consisting of the permanganate source and the carrier is also within the scope of the present disclosure. Similarly, although a permanganate source comprising or including a permanganate salt is described, permanganate sources consisting essentially of or consisting al a. permanganate salt are also within the scope of the disclosure. Thus, as described above, the composition may consist essentially of the permanganate source and the carrier. In this context, "consisting essentially of' RECU 13/5/215 22: 01 8E141223388270 PST
To: Page 53 of 58 2015-05-13 16:03:14 EDT
10036394262 From: Christine Graff PCT/US2014/037695 Replacement Sheet means that any additional components in the composition will not materially affect the corrosion resistance of a metal substrate including the composition. For example, a composition consisting essentially of a permanganate source and a carrier is free from anions other than permanganate.
100124] As used herein, unless otherwise expressly specified, all numbers such as those expressing values, ranges, amounts or percentages may be read as if prefaced by the word "about," even if the term does not expressly appear. Further, use of the word "about" reflects the penumbra of variation associated with measurement, significant figures, and interchangeability, all as understood by a person having ordinary skill in the art to which this disclosure pertains. Any numerical range recited herein is intended to include all sub-ranges subsumed therein. Plural encompasses singular and vice versa. For example, while the present disclosure describes "a"
permanganate source, a mixture of such permanganate sources can be used. When ranges are given, any endpoints of those ranges and/or numbers within those ranges can be combined within the scope of the present disclosure. The terms "including" and like terms mean "including but not limited to." Similarly, as used herein, the terms "on,"
"applied on,"
and "formed on" mean on, applied on, or formed on, but not necessarily in contact with the surface. For example, a composition ''applied on" a substrate does not preclude the presence of one or more other coating layers or compositions of the same or different composition located between the applied composition and the substrate.
[00125] Notwithstanding that the numerical ranges and parameters set forth herein may be approximations, numerical values set forth in the specific examples are reported as precisely as is practical. Any numerical value, however, inherently contains certain errors necessarily resulting from the standard variation found in their respective testing measurements. The word "comprising" and variations thereof as used in this description and in the claims do not limit the disclosure to exclude any =
variants or additions.
Claims (25)
1. A composition for application to a metal substrate, the composition comprising:
a carrier;
a permanganate anion source; and a corrosion inhibitor comprising a metal cation comprising a rare earth ion, an alkali metal ion, an alkaline earth metal ion, and/or a transition metal ion present in an amount of 0.0008 to 0.004 percent by weight of the composition.
a carrier;
a permanganate anion source; and a corrosion inhibitor comprising a metal cation comprising a rare earth ion, an alkali metal ion, an alkaline earth metal ion, and/or a transition metal ion present in an amount of 0.0008 to 0.004 percent by weight of the composition.
2. The composition according to claim 1, wherein the permanganate anion source comprises an alkali metal permanganate salt, and/or alkaline earth metal permanganate salt.
3. The composition according to claim 1, wherein the permanganate anion source comprises potassium permanganate.
4. The composition according to claim 1, further comprising an oxidizing agent.
5. The composition according to claim 4, wherein the oxidizing agent comprises hydrogen peroxide.
6. The composition according to claim 1, further comprising an azole compound.
7. The composition according to claim 6, wherein the azole compound comprises 2,5-dimercapto-1,3,4-thiadiazole, 1H-benzotriazole, 1H-1,2,3-triazole, 2-amino-mercapto-1,3,4-thiadiazole, and/or 2-amino-1,3,4-thiadiazole.
8. The composition according to claim 1, wherein the carrier comprises an aqueous carrier.
9. An article, comprising:
a substrate; and the composition of claim 1 on at least a portion of the substrate.
a substrate; and the composition of claim 1 on at least a portion of the substrate.
10. The article of claim 9, wherein the substrate comprises aluminum.
11. The article of claim 9, further comprising a coating on at least a portion of the composition.
12. A method of treating a substrate, the method comprising:
applying a first composition comprising the composition of claim 1 to the substrate to form a permanganate treated surface; and applying a second composition to the permanganate treated surface, the second composition comprising a lithium source and a second carrier.
applying a first composition comprising the composition of claim 1 to the substrate to form a permanganate treated surface; and applying a second composition to the permanganate treated surface, the second composition comprising a lithium source and a second carrier.
13. The method according to claim 12, wherein the permanganate anion source comprises an alkali metal permanganate salt and/or an alkaline earth metal permanganate salt.
14. The method according to claim 12, wherein the permanganate salt comprises potassium permanganate.
15. The method according to claim 12, wherein the lithium source comprises a lithium carbonate, a lithium hydroxide, and/or a lithium phosphate.
16. The method according to claim 12, wherein the second carrier comprises an aqueous carrier.
17. The method according to claim 12, further comprising applying a degreasing composition and/or a deoxidizing composition to the substrate prior to the applying the first composition to the substrate.
18. The method according to claim 12, wherein the lithium containing composition further comprises an azole compound.
19. The method according to claim 18, wherein the azole compound comprises 2,5-dimercapto-1,3,4-thiadiazole, 1H-benzotriazole, 1H-1,2,3-triazole, 2-amino-5-mercapto-1,3,4-thiadiazole, and/or 2-amino-1,3,4-thiadiazole.
20. A method of treating a substrate, the method comprising:
applying a cleaning composition to the substrate to form a cleaned substrate;
applying the composition of claim 1 to form a permanganate treated substrate;
and applying a second composition to the permanganate treated substrate, the second composition comprising a lithium source and a second carrier.
applying a cleaning composition to the substrate to form a cleaned substrate;
applying the composition of claim 1 to form a permanganate treated substrate;
and applying a second composition to the permanganate treated substrate, the second composition comprising a lithium source and a second carrier.
21. The method of claim 20, further comprising rinsing the cleaned substrate prior to the applying the first composition.
22. The method of claim 20, further comprising rinsing the permanganate treated substrate prior to applying the second composition.
23. The method of claim 20, wherein the second composition further comprises an indicator compound and/or an azole compound.
24. The method of claim 23, wherein the azole compound comprises 2,5-dimercapto-1,3,4-thiadiazole, 1H-benzotriazole, 1H-1,2,3-triazole, 2-amino-5-mercapto-1,3,4-thiadiazole, and/or 2-amino-1,3,4-thiadiazole.
25. The method of claim 20, wherein the applying the cleaning composition to the substrate comprises applying an acidic cleaning composition to the substrate and/or applying an alkaline cleaning composition to the substrate.
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PCT/US2014/037695 WO2014186286A1 (en) | 2013-05-14 | 2014-05-12 | Permanganate based conversion coating compositions |
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-
2014
- 2014-05-12 ES ES14730335T patent/ES2925233T3/en active Active
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- 2014-05-12 US US14/891,050 patent/US20160083849A1/en not_active Abandoned
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CA2912537A1 (en) | 2014-11-20 |
WO2014186286A1 (en) | 2014-11-20 |
AU2014265644B2 (en) | 2017-01-19 |
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US20160083849A1 (en) | 2016-03-24 |
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EP2997177A1 (en) | 2016-03-23 |
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JP2016526068A (en) | 2016-09-01 |
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BR112015028684A2 (en) | 2017-07-25 |
RU2015153430A (en) | 2017-06-19 |
JP2018197352A (en) | 2018-12-13 |
HK1215055A1 (en) | 2016-08-12 |
RU2631226C2 (en) | 2017-09-19 |
CN105339524A (en) | 2016-02-17 |
US11408077B2 (en) | 2022-08-09 |
ES2925233T3 (en) | 2022-10-14 |
KR20160008595A (en) | 2016-01-22 |
US20200354837A1 (en) | 2020-11-12 |
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